Molecular sieve catalyst composition, its making and use in conversion processes

ABSTRACT

The invention relates to a molecular sieve catalyst composition, to a method of making or forming the molecular sieve catalyst composition, and to a conversion process using the catalyst composition. In particular, the invention is directed to a molecular sieve catalyst composition of a molecular sieve, a binder and a matrix material, wherein the weight ratio of the binder to the molecular sieve is controlled to provide an improved attrition resistant catalyst composition, particularly useful in a conversion process for producing olefin(s), preferably ethylene and/or propylene, from a feedstock, preferably an oxygenate containing feedstock.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority from the provisional patentapplication U.S. Ser. No. 60/365,902, filed Mar. 22, 2002, which isherein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to a molecular sieve catalyst composition,to a method of making or forming the molecular sieve catalystcomposition, and to a conversion process using the catalyst composition.

BACKGROUND OF THE INVENTION

Olefins are traditionally produced from petroleum feedstock by catalyticor steam cracking processes. These cracking processes, especially steamcracking, produce light olefin(s) such as ethylene and/or propylene froma variety of hydrocarbon feedstock. Ethylene and propylene are importantcommodity petrochemicals useful in a variety of processes for makingplastics and other chemical compounds.

The petrochemical industry has known for some time that oxygenates,especially alcohols, are convertible into light olefin(s). There arenumerous technologies available for producing oxygenates includingfermentation or reaction of synthesis gas derived from natural gas,petroleum liquids, carbonaceous materials including coal, recycledplastics, municipal waste or any other organic material. Generally, theproduction of synthesis gas involves a combustion reaction of naturalgas, mostly methane, and an oxygen source into hydrogen, carbon monoxideand/or carbon dioxide. Syngas production processes are well known, andinclude conventional steam reforming, autothermal reforming, or acombination thereof.

Methanol, the preferred alcohol for light olefin production, istypically synthesized from the catalytic reaction of hydrogen, carbonmonoxide and/or carbon dioxide in a methanol reactor in the presence ofa heterogeneous catalyst. For example, in one synthesis process methanolis produced using a copper/zinc oxide catalyst in a water-cooled tubularmethanol reactor. The preferred methanol conversion process is generallyreferred to as a methanol-to-olefin(s) process, where methanol isconverted to primarily ethylene and/or propylene in the presence of amolecular sieve.

Molecular sieves are porous solids having pores of different sizes suchas zeolites or zeolite-type molecular sieves, carbons and oxides. Themost commercially useful molecular sieves for the petroleum andpetrochemical industries are known as zeolites, for examplealuminosilicate molecular sieves. Zeolites in general have a one-, two-or three-dimensional crystalline pore structure having uniformly sizedpores of molecular dimensions that selectively adsorb molecules that canenter the pores, and exclude those molecules that are too large.

There are many different types of molecular sieves well known to converta feedstock, especially an oxygenate containing feedstock, into one ormore olefin(s). For example, U.S. Pat. No. 5,367,100 describes the useof a well known zeolite, ZSM-5, to convert methanol into olefin(s); U.S.Pat. No. 4,062,905 discusses the conversion of methanol and otheroxygenates to ethylene and propylene using crystalline aluminosilicatezeolites, for example Zeolite T, ZK5, erionite and chabazite; U.S. Pat.No. 4,079,095 describes the use of ZSM-34 to convert methanol tohydrocarbon products such as ethylene and propylene; and U.S. Pat. No.4,310,440 describes producing light olefin(s) from an alcohol using acrystalline aluminophosphates, often represented by ALPO₄.

One of the most useful molecular sieves for converting methanol toolefin(s) is a silicoaluminophosphate molecular sieves.Silicoaluminophosphate (SAPO) molecular sieves contain athree-dimensional microporous crystalline framework structure of [SiO₂],[AlO₂] and [PO₂] corner sharing tetrahedral units. SAPO synthesis isdescribed in U.S. Pat. No. 4,440,871, which is herein fully incorporatedby reference. SAPO is generally synthesized by the hydrothermalcrystallization of a reaction mixture of silicon-, aluminum- andphosphorus-sources and at least one templating agent. Synthesis of aSAPO molecular sieve, its formulation into a SAPO catalyst, and its usein converting a hydrocarbon feedstock into olefin(s), particularly wherethe feedstock is methanol, is shown in U.S. Pat. Nos. 4,499,327,4,677,242, 4,677,243, 4,873,390, 5,095,163, 5,714,662 and 6,166,282, allof which are herein fully incorporated by reference.

Typically, molecular sieves are formed into molecular sieve catalystcompositions to improve their durability in commercial conversionprocesses. The collisions within a commercial process between catalystcomposition particles themselves, the reactor walls, and other reactorsystems cause the particles to breakdown into smaller particles calledfines. The physical breakdown of the molecular sieve catalystcomposition particles is known as attrition. Fines often exit thereactor in the effluent stream resulting in problems in recoverysystems. Catalyst compositions having a higher resistance to attritiongenerate fewer fines, less catalyst composition is required forconversion, and longer life times result in lower operating costs.

Molecular sieve catalyst compositions are formed by combining amolecular sieve and a matrix material usually in the presence of abinder. The purpose of the binder is hold the matrix material, often aclay, to the molecular sieve. The use of binders and matrix materials inthe formation of molecular sieve catalyst compositions is well known fora variety of commercial processes. It is also known that the way inwhich the molecular sieve catalyst composition is made or formulatedaffects catalyst composition attrition.

Example of methods of making catalyst compositions include: U.S. Pat.No. 5,126,298 discusses a method for making a cracking catalyst havinghigh attrition resistance by combining two different clay particles inseparate slurries with a zeolite slurry and a source of phosphorous, andspray drying a mixture of the slurries having a pH below 3; U.S. Pat.No. 4,987,110 and 5,298,153 relates to a catalytic cracking processusing a spray dried attrition resistant catalyst containing greater than25 weight percent molecular sieve dispersed in a clay matrix with asynthetic silica-alumina component; U.S. Pat. Nos. 5,194,412 and5,286,369 discloses forming a catalytic cracking catalyst of a molecularsieve and a crystalline aluminum phosphate binder having a surface arealess than 20 m²/g and a total pore volume less than 0.1 cc/g; U.S. Pat.No. 4,542,118 relates to forming a particulate inorganic oxide compositeof a zeolite and aluminum chlorhydrol that is reacted with ammonia toform a cohesive binder; U.S. Pat. No. 6,153,552 claims a method ofmaking a catalyst, by drying a slurry of a SAPO molecular sieve, aninorganic oxide sol, and an external phosphorous source; U.S. Pat. No.5,110,776 illustrates the formation of a zeolite containing catalyticcatalyst by modifying the zeolite with a phosphate containing solution;U.S. Pat. No. 5,348,643 relates to spray drying a zeolite slurry with aclay and source of phosphorous at a pH of below 3; U.S. patentapplication Ser. No. 09/891,674 filed Jun. 25, 2001 discusses a methodfor steaming a molecular sieve to remove halogen; U.S. Pat. No.5,248,647 illustrates spray drying a SAPO-34 molecular sieve admixedwith kaolin and a silica sol; U.S. Pat. No. 5,346,875 discloses a methodfor making a catalytic cracking catalyst by matching the isoelectricpoint of each component of the framework structure to the pH of theinorganic oxide sol; Mäurer, et al, Aggregation and Peptization Behaviorof Zeolite Crystals in Sols and Suspensions, Ind. Eng. Chem. Vol. 40,pages 2573-2579, 2001 discusses zeolite aggregation at or near theisoelectric point; PCT Publication WO 99/21651 describes making acatalyst by drying a mixture of an alumina sol and a SAPO molecularsieve; PCT Publication WO 02/05950 describes making a catalystcomposition of a molecular sieve containing attrition particles withfresh molecular sieve; and WO 02/05952 discloses a crystallinemetallo-aluminophosphate molecular sieve and a matrix material of aninorganic oxide binder and filler where the molecular sieve is presentin an amount less than 40 weight percent relative to the catalyst weightand a preferable weight ratio of the binder to molecular sieve close to1.

Although these molecular sieve catalyst compositions described above areuseful in hydrocarbon conversion processes, it would be desirable tohave an improved molecular sieve catalyst composition having betterattrition resistance and commercially desirable operability and costadvantages.

SUMMARY OF THE INVENTION

This invention provides for a method of making or formulating amolecular sieve catalyst composition and to its use in a conversionprocess for converting a feedstock into one or more olefin(s).

In one embodiment the invention is directed to a method for making amolecular sieve composition by combining, contacting, mixing, or thelike, a molecular sieve, a matrix material and a binder, wherein theweight ratio of binder to molecular sieve is greater than 0.1 to about0.5. In a preferred embodiment, the molecular sieve is synthesized fromthe combination from at least two of the group consisting of a siliconsource, a phosphorous source and an aluminum source, optionally in thepresence of a templating agent, more preferably the molecular sieve is asilicoaluminophosphate or aluminophosphate, and most preferably asilicoaluminophosphate.

In another embodiment the invention relates to a method for formulatinga molecular sieve catalyst composition, the method comprising the stepsof: (a) forming a slurry of a molecular sieve, a binder and a matrixmaterial wherein the weight ratio of the binder to the molecular sieveis greater than 0.1 to less than 0.5; (b) spray drying the slurry toproduce a formulated molecular sieve catalyst composition. In apreferred embodiment, the weight ratio of the binder to the molecularsieve is greater than 0.12 to less than 0.45, wherein the binder is analumina and the molecular sieve is a silicoaluminophosphate.

In another embodiment, the invention is directed to a molecular sievecatalyst composition comprising a molecular sieve, a binder and a matrixmaterial, wherein the weight ratio of the binder to the molecular sieveis in the range of greater than 0.1 to less than 0.5, preferably in therange greater than 0.12 to 0.45, and most preferably in the range offrom 0.13 to about 0.40. In yet another embodiment, the invention isdirected to the a formulated molecular sieve catalyst compositioncomprising the reaction product of at least one molecular sieve, atleast one binder, and optionally at least one matrix material, whereinthe weight ratio of the total weight of the binder to the total weightof the molecular sieve is in the range of from 0.11 to 0.45. Preferablythe molecular sieve is a silicoaluminophosphate, an aluminophosphateand/or a chabazite structure-type molecular sieve.

In yet another embodiment, the invention is directed to a process forproducing olefin(s) in the presence of any of the above molecular sievecatalyst compositions. In particular, the process involves producingolefin(s) in a process for converting a feedstock, preferably afeedstock containing an oxygenate, more preferably a feedstockcontaining an alcohol, and most preferably a feedstock containingmethanol in the presence of one or more of the molecular sieve catalystcompositions thereof.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The invention is directed toward a molecular sieve catalyst composition,its making and to its use in the conversion of a hydrocarbon feedstockinto one or more olefin(s). The molecular sieve catalyst composition ismade or formed from the combination of a molecular sieve, a binder, andoptionally, most preferably, a matrix material. It has been known in theart that varying the weight percent of the molecular sieve in the totalcatalyst composition is important. However, it has been surprisinglyfound that the weight ratio of the binder to the molecular sieve isimportant to making or forming an attrition resistance catalystcomposition. Without being bound to any particular theory it is believedthat when the weight ratio of the binder to molecular sieve is too highthen the surface area of the catalyst composition decreases resulting inlower conversion rates, and when the weight ratio of the binder tomolecular sieve is too low then the catalyst composition will breakapart into fines more easily.

Molecular Sieves and Catalysts Thereof

Molecular sieves have various chemical and physical, framework,characteristics. Molecular sieves have been well classified by theStructure Commission of the International Zeolite Association accordingto the rules of the IUPAC Commission on Zeolite Nomenclature. Aframework-type describes the connectivity, topology, of thetetrahedrally coordinated atoms constituting the framework, and makingan abstraction of the specific properties for those materials.Framework-type zeolite and zeolite-type molecular sieves for which astructure has been established, are assigned a three letter code and aredescribed in the Atlas of zeolite Framework Types, 5th edition,Elsevier, London, England (2001), which is herein fully incorporated byreference.

Non-limiting examples of these molecular sieves are the small poremolecular sieves, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI,DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG,THO, and substituted forms thereof; the medium pore molecular sieves,AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON, and substituted formsthereof; and the large pore molecular sieves, EMT, FAU, and substitutedforms thereof. Other molecular sieves include ANA, BEA, CFI, CLO, DON,GIS, LTL, MER, MOR, MWW and SOD. Non-limiting examples of the preferredmolecular sieves, particularly for converting an oxygenate containingfeedstock into olefin(s), include AEL, AFY, BEA, CHA, EDI, FAU, FER,GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON. In one preferredembodiment, the molecular sieve of the invention has an AEI topology ora CHA topology, or a combination thereof, most preferably a CHAtopology.

Molecular sieve materials all have 3-dimensional framework structure ofcorner-sharing TO₄ tetrahedra, where T is any tetrahedrally coordinatedcation. These molecular sieves are typically described in terms of thesize of the ring that defines a pore, where the size is based on thenumber of T atoms in the ring. Other framework-type characteristicsinclude the arrangement of rings that form a cage, and when present, thedimension of channels, and the spaces between the cages. See van Bekkum,et al., Introduction to Zeolite Science and Practice, Second CompletelyRevised and Expanded Edition, Volume 137, pages 1-67, Elsevier Science,B.V., Amsterdam, Netherlands (2001).

The small, medium and large pore molecular sieves have from a 4-ring toa 12-ring or greater framework-type. In a preferred embodiment, thezeolitic molecular sieves have 8-, 10- or 12-ring structures or largerand an average pore size in the range of from about 3 Å to 15 Å. In themost preferred embodiment, the molecular sieves of the invention,preferably silicoaluminophosphate molecular sieves have 8-rings and anaverage pore size less than about 5 Å, preferably in the range of from 3Å to about 5 Å, more preferably from 3 Å to about 4.5 Å, and mostpreferably from 3.5 Å to about 4.2 Å.

Molecular sieves, particularly zeolitic and zeolitic-type molecularsieves, preferably have a molecular framework of one, preferably two ormore corner-sharing [TO₄] tetrahedral units, more preferably, two ormore [SiO₄], [AlO₄] and/or [PO₄] tetrahedral units, and most preferably[SiO₄], [AlO₄] and [PO₄] tetrahedral units. These silicon, aluminum, andphosphorous based molecular sieves and metal containing silicon,aluminum and phosphorous based molecular sieves have been described indetail in numerous publications including for example, U.S. Pat. No.4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), U.S. Pat. No. 4,440,871(SAPO), European Patent Application EP-A-0 159 624 (ELAPSO where El isAs, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S. Pat. No.4,554,143 (FeAPO), U.S. Pat. Nos. 4,822,478, 4,683,217, 4,744,885(FeAPSO), EP-A-0 158 975 and U.S. Pat. No. 4,935,216 (ZnAPSO, EP-A-0 161489 (CoAPSO), EP-A-0 158 976 (ELAPO, where EL is Co, Fe, Mg, Mn, Ti orZn), U.S. Pat. No. 4,310,440 (AlPO₄), EP-A-0 158 350 (SENAPSO), U.S.Pat. No. 4,973,460 (LiAPSO), U.S. Pat. No. 4,789,535 (LiAPO), U.S. Pat.No. 4,992,250 (GeAPSO), U.S. Pat. No. 4,888,167 (GeAPO), U.S. Pat. No.5,057,295 (BAPSO), U.S. Pat. No. 4,738,837 (CrAPSO), U.S. Pat. Nos.4,759,919, and 4,851,106 (CrAPO), U.S. Pat. Nos. 4,758,419, 4,882,038,5,434,326 and 5,478,787 (MgAPSO), U.S. Pat. No. 4,554,143 (FeAPO), U.S.Pat. No. 4,894,213 (AsAPSO), U.S. Pat. No. 4,913,888 (AsAPO), U.S. Pat.Nos. 4,686,092, 4,846,956 and 4,793,833 (MnAPSO), U.S. Pat. Nos.5,345,011 and 6,156,931 (MnAPO), U.S. Pat. No. 4,737,353 (BeAPSO), U.S.Pat. No. 4,940,570 (BeAPO), U.S. Pat. Nos. 4,801,309, 4,684,617 and4,880,520 (TiAPSO), U.S. Pat. Nos. 4,500,651, 4,551,236 and 4,605,492(TiAPO), U.S. Pat. Nos. 4,824,554, 4,744,970 (CoAPSO), U.S. Pat. No.4,735,806 (GaAPSO) EP-A-0 293 937 (QAPSO, where Q is framework oxideunit [QO₂]), as well as U.S. Pat. Nos. 4,567,029, 4,686,093, 4,781,814,4,793,984, 4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,956,164,4,956,165, 4,973,785, 5,241,093, 5,493,066 and 5,675,050, all of whichare herein fully incorporated by reference. Other molecular sieves aredescribed in R. Szostak, Handbook of Molecular Sieves, Van NostrandReinhold, New York, N.Y. (1992), which is herein fully incorporated byreference.

The more preferred silicon, aluminum and/or phosphorous containingmolecular sieves, and aluminum, phosphorous, and optionally silicon,containing molecular sieves include aluminophosphate (ALPO) molecularsieves and silicoaluminophosphate (SAPO) molecular sieves andsubstituted, preferably metal substituted, ALPO and SAPO molecularsieves. The most preferred molecular sieves are SAPO molecular sieves,and metal substituted SAPO molecular sieves. In an embodiment, the metalis an alkali metal of Group IA of the Periodic Table of Elements, analkaline earth metal of Group IIA of the Periodic Table of Elements, arare earth metal of Group IIIB, including the Lanthamides: lanthanum,cerium, praseodymium, neodymium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;and scandium or yttrium of the Periodic Table of Elements, a transitionmetal of Groups IVB, VB, VIIB, VIIB, VIIB, and IB of the Periodic Tableof Elements, or mixtures of any of these metal species. In one preferredembodiment, the metal is selected from the group consisting of Co, Cr,Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr, and mixtures thereof. Inanother preferred embodiment, these metal atoms discussed above areinserted into the framework of a molecular sieve through a tetrahedralunit, such as [MeO₂], and carry a net charge depending on the valencestate of the metal substituent. For example, in one embodiment, when themetal substituent has a valence state of +2, +3, +4, +5, or +6, the netcharge of the tetrahedral unit is between −2 and +2.

In one embodiment, the molecular sieve, as described in many of the U.S.Patents mentioned above, is represented by the empirical formula, on ananhydrous basis:mR:(M_(x)Al_(y)P_(z))O₂wherein R represents at least one templating agent, preferably anorganic templating agent; m is the number of moles of R per mole of(M_(x)Al_(y)P_(z))O₂ and m has a value from 0 to 1, preferably 0 to 0.5,and most preferably from 0 to 0.3; x, y, and z represent the molefraction of Al, P and M as tetrahedral oxides, where M is a metalselected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIIB, VIIB, VIIIBand Lanthamide's of the Periodic Table of Elements, preferably M isselected from one of the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg,Mn, Ni, Sn, Ti, Zn and Zr. In an embodiment, m is greater than or equalto 0.2, and x, y and z are greater than or equal to 0.01. In anotherembodiment, m is greater than 0.1 to about 1, x is greater than 0 toabout 0.25, y is in the range of from 0.4 to 0.5, and z is in the rangeof from 0.25 to 0.5, more preferably m is from 0.15 to 0.7, x is from0.01 to 0.2, y is from 0.4 to 0.5, and z is from 0.3 to 0.5.

Non-limiting examples of SAPO and ALPO molecular sieves of the inventioninclude one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16,SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37,SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. Pat. No. 6,162,415), SAPO-47,SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37,ALPO-46, and metal containing molecular sieves thereof. The morepreferred zeolite-type molecular sieves include one or a combination ofSAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, evenmore preferably one or a combination of SAPO-18, SAPO-34, ALPO-34 andALPO-18, and metal containing molecular sieves thereof, and mostpreferably one or a combination of SAPO-34 and ALPO-18, and metalcontaining molecular sieves thereof.

In an embodiment, the molecular sieve is an intergrowth material havingtwo or more distinct phases of crystalline structures within onemolecular sieve composition. In particular, intergrowth molecular sievesare described in the U.S. patent application Ser. No. 09/924,016 filedAug. 7, 2001 and PCT WO 98/15496 published Apr. 16, 1998, both of whichare herein fully incorporated by reference. For example, SAPO-18,ALPO-18 and RUW-18 have an AEI framework-type, and SAPO-34 has a CHAframework-type. In another embodiment, the molecular sieve comprises atleast one intergrown phase of AEI and CHA framework-types, preferablythe molecular sieve has a greater amount of CHA framework-type to AEIframework-type, and more preferably the ratio of, CHA to AEI is greaterthan 1:1.

Molecular Sieve Synthesis

The synthesis of molecular sieves is described in many of the referencesdiscussed above. Generally, molecular sieves are synthesized by thehydrothermal crystallization of one or more of a source of aluminum, asource of phosphorous, a source of silicon, a templating agent, and ametal containing compound. Typically, a combination of sources ofsilicon, aluminum and phosphorous, optionally with one or moretemplating agents and/or one or more metal containing compounds areplaced in a sealed pressure vessel, optionally lined with an inertplastic such as polytetrafluoroethylene, and heated, under acrystallization pressure and temperature, until a crystalline materialis formed, and then recovered by filtration, centrifugation and/ordecanting.

In a preferred embodiment the molecular sieves are synthesized byforming a reaction product of a source of silicon, a source of aluminum,a source of phosphorous, an organic templating agent, preferably anitrogen containing organic templating agent. This particularlypreferred embodiment results in the synthesis of asilicoaluminophosphate crystalline material that is then isolated byfiltration, centrifugation and/or decanting.

Non-limiting examples of silicon sources include a silicates, fumedsilica, for example, Aerosil-200 available from Degussa Inc., New York,N.Y., and CAB-O-SIL M-5, silicon compounds such as tetraalkylorthosilicates, for example, tetramethyl orthosilicate (TMOS) andtetraethylorthosilicate (TEOS), colloidal silicas or aqueous suspensionsthereof, for example Ludox-HS-40 sol available from E.I. du Pont deNemours, Wilmington, Del., silicic acid, alkali-metal silicate, or anycombination thereof. The preferred source of silicon is a silica sol.

Non-limiting examples of aluminum sources include aluminum-containingcompositions such as aluminum alkoxides, for example aluminumisopropoxide, aluminum phosphate, aluminum hydroxide, sodium aluminate,pseudo-boehmite, gibbsite and aluminum trichloride, or any combinationsthereof. A preferred source of aluminum is pseudo-boehmite, particularlywhen producing a silicoaluminophosphate molecular sieve.

Non-limiting examples of phosphorous sources, which may also includealuminum-containing phosphorous compositions, includephosphorous-containing, inorganic or organic, compositions such asphosphoric acid, organic phosphates such as triethyl phosphate, andcrystalline or amorphous aluminophosphates such as ALPO₄, phosphoroussalts, or combinations thereof. The preferred source of phosphorous isphosphoric acid, particularly when producing a silicoaluminophosphate.

Templating agents are generally compounds that contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen, phosphorus,arsenic and antimony, more preferably nitrogen or phosphorous, and mostpreferably nitrogen. Typical templating agents of Group VA of thePeriodic Table of elements also contain at least one alkyl or arylgroup, preferably an alkyl or aryl group having from 1 to 10 carbonatoms, and more preferably from 1 to 8 carbon atoms. The preferredtemplating agents are nitrogen-containing compounds such as amines andquaternary ammonium compounds.

The quaternary ammonium compounds, in one embodiment, are represented bythe general formula R₄N⁺, where each R is hydrogen or a hydrocarbyl orsubstituted hydrocarbyl group, preferably an alkyl group or an arylgroup having from 1 to 10 carbon atoms. In one embodiment, thetemplating agents include a combination of one or more quaternaryammonium compound(s) and one or more of a mono-, di- or tri-amine.

Non-limiting examples of templating agents include tetraalkyl ammoniumcompounds including salts thereof such as tetramethyl ammonium compoundsincluding salts thereof, tetraethyl ammonium compounds including saltsthereof, tetrapropyl ammonium including salts thereof, andtetrabutylammonium including salts thereof, cyclohexylamine, morpholine,di-n-propylamine (DPA), tripropylamine, triethylamine (TEA),triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine,N,N-dimethylbenzylamine, N,N-diethylethanolamine, dicyclohexylamine,N,N-dimethylethanolamine, choline, N,N′-dimethylpiperazine,1,4-diazabicyclo(2,2,2)octane, N′,N′,N,N-tetramethyl-(1,6)hexanediamine,N-methyldiethanolamine, N-methyl-ethanolamine, N-methyl piperidine,3-methyl-piperidine, N-methylcyclohexylamine, 3-methylpyridine,4-methyl-pyridine, quinuclidine, N,N′-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine, neopentylamine, di-n-pentylamine,isopropylamine, t-butyl-amine, ethylenediamine, pyrrolidine, and2-imidazolidone.

The preferred templating agent or template is a tetraethylammoniumcompound, such as tetraethyl ammonium hydroxide (TEAOH), tetraethylammonium phosphate, tetraethyl ammonium fluoride, tetraethyl ammoniumbromide, tetraethyl ammonium chloride and tetraethyl ammonium acetate.The most preferred templating agent is tetraethyl ammonium hydroxide andsalts thereof, particularly when producing a silicoaluminophosphatemolecular sieve. In one embodiment, a combination of two or more of anyof the above templating agents is used in combination with one or moreof a silicon-, aluminum-, and phosphorous-source.

A synthesis mixture containing at a minimum a silicon-, aluminum-,and/or phosphorous-composition, and a templating agent, should have a pHin the range of from 2 to 10, preferably in the range of from 4 to 9,and most preferably in the range of from 5 to 8. Generally, thesynthesis mixture is sealed in a vessel and heated, preferably underautogenous pressure, to a temperature in the range of from about 80° C.to about 250° C., and more preferably from about 150° C. to about 180°C. The time required to form the crystalline product is typically fromimmediately up to several weeks, the duration of which is usuallydependent on the temperature; the higher the temperature the shorter theduration. Typically, the crystalline molecular sieve product is formed,usually in a slurry state, and is recovered by any standard techniquewell known in the art, for example centrifugation or filtration. Theisolated or separated crystalline product, in an embodiment, is washed,typically, using a liquid such as water, from one to many times. Thewashed crystalline product is then optionally dried, preferably in air.

In one preferred embodiment, when a templating agent is used in thesynthesis of a molecular sieve, it is preferred that the templatingagent is substantially, preferably completely, removed aftercrystallization by numerous well known techniques, for example, heattreatments such as calcination. Calcination involves contacting themolecular sieve containing the templating agent with a gas, preferablycontaining oxygen, at any desired concentration at an elevatedtemperature sufficient to either partially or completely decompose andoxidize the templating agent.

Molecular sieves have either a high silicon (Si) to aluminum (Al) ratioor a low silicon to aluminum ratio, however, a low Si/Al ratio ispreferred for SAPO synthesis. In one embodiment, the molecular sieve hasa Si/As ratio less than 0.65, preferably less than 0.40, more preferablyless than 0.32, and most preferably less than 0.20. In anotherembodiment the molecular sieve has a Si/Al ratio in the range of fromabout 0.65 to about 0.10, preferably from about 0.40 to about 0.10, morepreferably from about 0.32 to about 0.10, and more preferably from about0.32 to about 0.15.

Method for Making Molecular Sieve Catalyst Compositions

Once the molecular sieve is synthesized, depending on the requirementsof the particular conversion process, the molecular sieve is thenformulated into a molecular sieve catalyst composition, particularly forcommercial use. The molecular sieves synthesized above are made orformulated into molecular sieve catalyst compositions by combining thesynthesized molecular sieve(s) with a binder and optionally, butpreferably, a matrix material to form a molecular sieve catalystcomposition or a formulated molecular sieve catalyst composition. Thisformulated molecular sieve catalyst composition is formed into usefulshape and sized particles by well-known techniques such as spray drying,pelletizing, extrusion, and the like.

In one embodiment, the weight ratio of the binder to the molecular sieveis in the range of from about 0.1 to 0.5, preferably in the range offrom 0.1 to less than 0.5, more preferably in the range of from 0.11 to0.48, even more preferably from 0.12 to about 0.45, yet even morepreferably from 0.13 to less than 0.45, and most preferably in the rangeof from 0.15 to about 0.4. In another embodiment, the weight ratio ofthe binder to the molecular sieve is in the range of from 0.11 to 0.45,preferably in the range of from about 0.12 to less than 0.40, morepreferably in the range of from 0.15 to about 0.35, and most preferablyin the range of from 0.2 to about 0.3. All values between these rangesare included in this patent specification.

In another embodiment, the molecular sieve catalyst composition orformulated molecular sieve catalyst composition has a micropore surfacearea (MSA) measured in m²/g-molecular sieve that is about 70 percent,preferably about 75 percent, more preferably 80 percent, even morepreferably 85 percent, and most preferably about 90 percent of the MSAof the molecular sieve itself. In one embodiment, the catalystcomposition has a MSA in the range of from 400 m²/g-molecular sieve toabout 600 m²/g-molecular sieve, preferably MSA in the range of from 425m²/g-molecular sieve to about 575 m²/g-molecular, more preferably in therange of from 425 m²/g-molecular sieve to about 550 m²/g-molecularsieve, and most preferably in the range of from about 450 m²/g-molecularsieve to about 550 m²/g-molecular sieve.

There are many different binders that are useful in forming themolecular sieve catalyst composition. Non-limiting examples of bindersthat are useful alone or in combination include various types ofhydrated alumina, silicas, and/or other inorganic oxide sol. Onepreferred alumina containing sol is aluminum chlorhydrate. The inorganicoxide sol acts like glue binding the synthesized molecular sieves andother materials such as the matrix together, particularly after thermaltreatment. Upon heating, the inorganic oxide sol, preferably having alow viscosity, is converted into an inorganic oxide matrix component.For example, an alumina sol will convert to an aluminum oxide matrixfollowing heat treatment.

Aluminum chlorhydrate, a hydroxylated aluminum based sol containing achloride counter ion, has the general formula ofAl_(m)O_(n)(OH)_(o)Cl_(p).x(H₂O) wherein m is 1 to 20, n is 1 to 8, o is5 to 40, p is 2 to 15, and x is 0 to 30. In one embodiment, the binderis Al₁₃O₄(OH)₂₄Cl₇.12(H₂O) as is described in G. M. Wolterman, et al.,Stud. Surf. Sci. and Catal., 76, pages 105-144 (1993), which is hereinincorporated by reference. In another embodiment, one or more bindersare combined with one or more other non-limiting examples of aluminamaterials such as aluminum oxyhydroxide, γ-alumina, boehmite, diaspore,and transitional aluminas such as α-alumina, β-alumina, γ-alumina,δ-alumina, ε-alumina, κ-alumina, and ρ-alumina, aluminum trihydroxide,such as gibbsite, bayerite, nordstrandite, doyelite, and mixturesthereof.

In another embodiment, the binders are alumina sols, predominantlycomprising aluminum oxide, optionally including some silicon. In yetanother embodiment, the binders are peptized alumina made by treatingalumina hydrates such as pseudobohemite, with an acid, preferably anacid that does not contain a halogen, to prepare sols or aluminum ionsolutions. Non-limiting examples of commercially available colloidalalumina sols include Nalco 8676 available from Nalco Chemical Co.,Naperville, Ill., and Nyacol available from The PQ Corporation, ValleyForge, Pa.

The molecular sieve compositions described above, in a preferredembodiment, is combined with one or more matrix material(s). Matrixmaterials are typically effective in reducing overall catalyst cost, actas thermal sinks assisting in shielding heat from the catalystcomposition for example during regeneration, densifying the catalystcomposition, increasing catalyst strength such as crush strength andattrition resistance, and to control the rate of conversion in aparticular process.

Non-limiting examples of matrix materials include one or more of: rareearth metals, non-active, metal oxides including titania, zirconia,magnesia, thoria, beryllia, quartz, silica or sols, and mixturesthereof, for example silica-magnesia, silica-zirconia, silica-titania,silica-alumina and silica-alumina-thoria. In an embodiment, matrixmaterials are natural clays such as those from the families ofmontmorillonite and kaolin. These natural clays include sabbentonitesand those kaolins known as, for example, Dixie, McNamee, Georgia andFlorida clays. Non-limiting examples of other matrix materials include:haloysite, kaolinite, dickite, nacrite, or anauxite. In one embodiment,the matrix material, preferably any of the clays, are subjected to wellknown modification processes such as calcination and/or acid treatmentand/or chemical treatment.

In one preferred embodiment, the matrix material is a clay or aclay-type composition, preferably the clay or clay-type compositionhaving a low iron or titania content, and most preferably the matrixmaterial is kaolin. Kaolin has been found to form a pumpable, high solidcontent slurry, it has a low fresh surface area, and it packs togethereasily due to its platelet structure. A preferred average particle sizeof the matrix material, most preferably kaolin, is from about 0.1 μm toabout 0.6 μm with a d₉₀ particle size distribution of less than about 1μm.

In one embodiment, the binder, the molecular sieve composition and thematrix material are combined in the presence of a liquid to form amolecular sieve catalyst composition, where the amount of binder is fromabout 2% by weight to about 30% by weight, preferably from about 5% byweight to about 20% by weight, and more preferably from about 7% byweight to about 15% by weight, based on the total weight of the binder,the molecular sieve and matrix material, excluding the liquid.

Upon combining the molecular sieve composition and the matrix material,optionally with a binder, in a liquid to form a slurry, mixing,preferably rigorous mixing is needed to produce a substantiallyhomogeneous mixture containing the molecular sieve composition.Non-limiting examples of suitable liquids include one or a combinationof water, alcohol, ketones, aldehydes, and/or esters. The most preferredliquid is water. In one embodiment, the slurry is colloid-milled for aperiod of time sufficient to produce the desired slurry texture,sub-particle size, and/or sub-particle size distribution.

The molecular sieve composition and matrix material, and the optionalbinder, are in the same or different liquid, and are combined in anyorder, together, simultaneously, sequentially, or a combination thereof.In the preferred embodiment, the same liquid, preferably water is used.The molecular sieve composition, matrix material, and optional binder,are combined in a liquid as solids, substantially dry or in a driedform, or as slurries, together or separately. If solids are addedtogether as dry or substantially dried solids, it is preferable to add alimited and/or controlled amount of liquid.

In one embodiment, the slurry of the molecular sieve composition, binderand matrix materials is mixed or milled to achieve a sufficientlyuniform slurry of sub-particles of the molecular sieve catalystcomposition that is then fed to a forming unit that produces themolecular sieve catalyst composition. In a preferred embodiment, theforming unit is spray dryer. Typically, the forming unit is maintainedat a temperature sufficient to remove most of the liquid from theslurry, and from the resulting molecular sieve catalyst composition. Theresulting catalyst composition when formed in this way takes the form ofmicrospheres.

When a spray drier is used as the forming unit, typically, the slurry ofthe molecular sieve composition and matrix material, and optionally abinder, is co-fed to the spray drying volume with a drying gas with anaverage inlet temperature ranging from 200° C. to 550° C., and acombined outlet temperature ranging from 100° C. to about 225° C. In anembodiment, the average diameter of the spray dried formed catalystcomposition is from about 40 μm to about 300 μm, preferably from about50 μm to about 250 μm, more preferably from about 50 μm to about 200 μm,and most preferably from about 65 μm to about 90 μm.

During spray drying, the slurry is passed through a nozzle distributingthe slurry into small droplets, resembling an aerosol spray into adrying chamber. Atomization is achieved by forcing the slurry through asingle nozzle or multiple nozzles with a pressure drop in the range offrom 100 psia to 1000 psia (690 kPaa to 6895 kpaa). In anotherembodiment, the slurry is co-fed through a single nozzle or multiplenozzles along with an atomization fluid such as air, steam, flue gas, orany other suitable gas.

In yet another embodiment, the slurry described above is directed to theperimeter of a spinning wheel that distributes the slurry into smalldroplets, the size of which is controlled by many factors includingslurry viscosity, surface tension, flow rate, pressure, and temperatureof the slurry, the shape and dimension of the nozzle(s), or the spinningrate of the wheel. These droplets are then dried in a co-current orcounter-current flow of air passing through a spray drier to form asubstantially dried or dried molecular sieve catalyst composition, morespecifically a molecular sieve composition in powder form.

Generally, the size of the powder is controlled to some extent by thesolids content of the slurry. However, control of the size of thecatalyst composition and its spherical characteristics are controllableby varying the slurry feed properties and conditions of atomization.

Other methods for forming a molecular sieve catalyst composition isdescribed in U.S. patent application Ser. No. 09/617,714 filed Jul. 17,2000 (spray drying using a recycled molecular sieve catalystcomposition), which is herein incorporated by reference.

In another embodiment, the formulated molecular sieve catalystcomposition contains from about 1% to about 99%, preferably from about10% to about 90%, more preferably from about 10% to about 80%, even morepreferably from about 20% to about 70%, and most preferably from about25% to about 60% by weight of the molecular sieve based on the totalweight of the molecular sieve catalyst composition.

Once the molecular sieve catalyst composition is formed in asubstantially dry or dried state, to further harden and/or activate theformed catalyst composition, a heat treatment such as calcination, at anelevated temperature is usually performed. A conventional calcinationenvironment is air that typically includes a small amount of watervapor. Typical calcination temperatures are in the range from about 400°C. to about 1,000° C., preferably from about 500° C. to about 800° C.,and most preferably from about 550° C. to about 700° C., preferably in acalcination environment such as air, nitrogen, helium, flue gas(combustion product lean in oxygen), or any combination thereof. In oneembodiment, calcination of the formulated molecular sieve catalystcomposition is carried out in any number of well known devices includingrotary calciners, fluid bed calciners, batch ovens, and the like.Calcination time is typically dependent on the degree of hardening ofthe molecular sieve catalyst composition and the temperature ranges fromabout 15 minutes to about 20 hours. In a preferred embodiment, themolecular sieve catalyst composition is heated in nitrogen at atemperature of from about 600° C. to about 700° C. Heating is carriedout for a period of time typically from 30 minutes to 15 hours,preferably from 1 hour to about 10 hours, more preferably from about 1hour to about 5 hours, and most preferably from about 2 hours to about 4hours.

In one embodiment, the attrition resistance of a molecular sievecatalyst composition is measured using an Attrition Rate Index (ARI),measured in weight percent catalyst composition attrited per hour. ARIis measured by adding 6.0 g of catalyst composition having a particlessize ranging from 53 microns to 125 microns to a hardened steelattrition cup. Approximately 23,700 cc/min of nitrogen gas is bubbledthrough a water-containing bubbler to humidify the nitrogen. The wetnitrogen passes through the attrition cup, and exits the attritionapparatus through a porous fiber thimble. The flowing nitrogen removesthe finer particles, with the larger particles being retained in thecup. The porous fiber thimble separates the fine catalyst particles fromthe nitrogen that exits through the thimble. The fine particlesremaining in the thimble represent the catalyst composition that hasbroken apart through attrition. The nitrogen flow passing through theattrition cup is maintained for 1 hour. The fines collected in thethimble are removed from the unit. A new thimble is then installed. Thecatalyst left in the attrition unit is attrited for an additional 3hours, under the same gas flow and moisture levels. The fines collectedin the thimble are recovered. The collection of fine catalyst particlesseparated by the thimble after the first hour are weighed. The amount ingrams of fine particles divided by the original amount of catalystcharged to the attrition cup expressed on per hour basis is the ARI, inweight percent per hour (wt. %/hr). ARI is represented by the formula:ARI=C/(B+C)/D multiplied by 100%, wherein B is weight of catalystcomposition left in the cup after the attrition test, C is the weight ofcollected fine catalyst particles after the first hour of attritiontreatment, and D is the duration of treatment in hours after the firsthour attrition treatment.

In one embodiment, the molecular sieve catalyst composition orformulated molecular sieve catalyst composition has an ARI less than 15weight percent per hour, preferably less than 10 weight percent perhour, more preferably less than 5 weight percent per hour, and even morepreferably less than 2 weight percent per hour, and most preferably lessthan 1 weight percent per hour. In one embodiment, the molecular sievecatalyst composition or formulated molecular sieve catalyst compositionhas an ARI in the range of from 0.1 weight percent per hour to less than5 weight percent per hour, more preferably from about 0.2 weight percentper hour to less than 3 weight percent per hour, and most preferablyfrom about 0.2 weight percent per hour to less than 2 weight percent perhour.

In one preferred embodiment of the invention, the molecular sievecatalyst composition or formulated molecular sieve catalyst compositioncomprises a molecular sieve in an amount of from 20 weight percent to 60weight percent, a binder in an amount of from 5 to 50 weight percent,and a matrix material in an amount of from 0 to 78 weight percent basedon the total weight of the catalyst composition, upon calcination, andthe catalyst composition having weight ratio of binder to sieve of from0.1 to less than 0.5. In addition, the catalyst composition of thisembodiment has surface area from 450 m²/g-molecular sieve to 550m²/g-molecular sieve, and/or an ARI less than 2 weight percent per hour.

Process For Using the Molecular Sieve Catalyst Compositions

The molecular sieve catalyst compositions described above are useful ina variety of processes including: cracking, of for example a naphthafeed to light olefin(s) (U.S. Pat. No. 6,300,537) or higher molecularweight (MW) hydrocarbons to lower MW hydrocarbons; hydrocracking, of forexample heavy petroleum and/or cyclic feedstock; isomerization, of forexample aromatics such as xylene, polymerization, of for example one ormore olefin(s) to produce a polymer product; reforming; hydrogenation;dehydrogenation; dewaxing, of for example hydrocarbons to removestraight chain paraffins; absorption, of for example alkyl aromaticcompounds for separating out isomers thereof; alkylation, of for examplearomatic hydrocarbons such as benzene and alkyl benzene, optionally withpropylene to produce cumeme or with long chain olefins; transalkylation,of for example a combination of aromatic and polyalkylaromatichydrocarbons; dealkylation; hydrodecylization; disproportionation, offor example toluene to make benzene and paraxylene; oligomerization, offor example straight and branched chain olefin(s); anddehydrocyclization.

Preferred processes are conversion processes including: naphtha tohighly aromatic mixtures; light olefin(s) to gasoline, distillates andlubricants; oxygenates to olefin(s); light paraffins to olefins and/oraromatics; and unsaturated hydrocarbons (ethylene and/or acetylene) toaldehydes for conversion into alcohols, acids and esters. The mostpreferred process of the invention is a process directed to theconversion of a feedstock comprising one or more oxygenates to one ormore olefin(s).

The molecular sieve catalyst compositions described above areparticularly useful in conversion processes of different feedstock.Typically, the feedstock contains one or more aliphatic-containingcompounds that include alcohols, amines, carbonyl compounds for examplealdehydes, ketones and carboxylic acids, ethers, halides, mercaptans,sulfides, and the like, and mixtures thereof. The aliphatic moiety ofthe aliphatic-containing compounds typically contains from 1 to about 50carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.

Non-limiting examples of aliphatic-containing compounds include:alcohols such as methanol and ethanol, alkyl-mercaptans such as methylmercaptan and ethyl mercaptan, alkyl-sulfides such as methyl sulfide,alkyl-amines such as methyl amine, alkyl-ethers such as dimethyl ether,diethyl ether and methylethyl ether, alkyl-halides such as methylchloride and ethyl chloride, alkyl ketones such as dimethyl ketone,formaldehydes, and various acids such as acetic acid.

In a preferred embodiment of the process of the invention, the feedstockcontains one or more oxygenates, more specifically, one or more organiccompound(s) containing at least one oxygen atom. In the most preferredembodiment of the process of invention, the oxygenate in the feedstockis one or more alcohol(s), preferably aliphatic alcohol(s) where thealiphatic moiety of the alcohol(s) has from 1 to 20 carbon atoms,preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4carbon atoms. The alcohols useful as feedstock in the process of theinvention include lower straight and branched chain aliphatic alcoholsand their unsaturated counterparts.

Non-limiting examples of oxygenates include methanol, ethanol,n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethylether, di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethylketone, acetic acid, and mixtures thereof. In the most preferredembodiment, the feedstock is selected from one or more of methanol,ethanol, dimethyl ether, diethyl ether or a combination thereof, morepreferably methanol and dimethyl ether, and most preferably methanol.

The various feedstocks discussed above, particularly a feedstockcontaining an oxygenate, more particularly a feedstock containing analcohol, is converted primarily into one or more olefin(s). Theolefin(s) or olefin monomer(s) produced from the feedstock typicallyhave from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, morepreferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbonsatoms, and most preferably ethylene an/or propylene. Non-limitingexamples of olefin monomer(s) include ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1,preferably ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1,hexene-1, octene-1 and isomers thereof. Other olefin monomer(s) includeunsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugatedor nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.

In the most preferred embodiment, the feedstock, preferably of one ormore oxygenates, is converted in the presence of a molecular sievecatalyst composition of the invention into olefin(s) having 2 to 6carbons atoms, preferably 2 to 4 carbon atoms. Most preferably, theolefin(s), alone or combination, are converted from a feedstockcontaining an oxygenate, preferably an alcohol, most preferablymethanol, to the preferred olefin(s) ethylene and/or propylene.

The are many processes used to convert feedstock into olefin(s)including various cracking processes such as steam cracking, thermalregenerative cracking, fluidized bed cracking, fluid catalytic cracking,deep catalytic cracking, and visbreaking. The most preferred process isgenerally referred to as gas-to-olefins (GTO) or alternatively,methanol-to-olefins (MTO). In a MTO process, typically an oxygenatedfeedstock, most preferably a methanol containing feedstock, is convertedin the presence of a molecular sieve catalyst composition thereof intoone or more olefin(s), preferably and predominantly, ethylene and/orpropylene, often referred to as light olefin(s).

In one embodiment of the process for conversion of a feedstock,preferably a feedstock containing one or more oxygenates, the amount ofolefin(s) produced based on the total weight of hydrocarbon produced isgreater than 50 weight percent, preferably greater than 60 weightpercent, more preferably greater than 70 weight percent, and mostpreferably greater than 75 weight percent. In another embodiment of theprocess for conversion of one or more oxygenates to one or moreolefin(s), the amount of ethylene and/or propylene produced based on thetotal weight of hydrocarbon product produced is greater than 65 weightpercent, preferably greater than 70 weight percent, more preferablygreater than 75 weight percent, and most preferably greater than 78weight percent.

In another embodiment of the process for conversion of one or moreoxygenates to one or more olefin(s), the amount ethylene produced inweight percent based on the total weight of hydrocarbon productproduced, is greater than 30 weight percent, more preferably greaterthan 35 weight percent, and most preferably greater than 40 weightpercent. In yet another embodiment of the process for conversion of oneor more oxygenates to one or more olefin(s), the amount of propyleneproduced in weight percent based on the total weight of hydrocarbonproduct produced is greater than 20 weight percent, preferably greaterthan 25 weight percent, more preferably greater than 30 weight percent,and most preferably greater than 35 weight percent.

The feedstock, in one embodiment, contains one or more diluents),typically used to reduce the concentration of the feedstock, and aregenerally non-reactive to the feedstock or molecular sieve catalystcomposition. Non-limiting examples of diluents include helium, argon,nitrogen, carbon monoxide, carbon dioxide, water, essentiallynon-reactive paraffins (especially alkanes such as methane, ethane, andpropane), essentially non-reactive aromatic compounds, and mixturesthereof. The most preferred diluents are water and nitrogen, with waterbeing particularly preferred.

The diluent, water, is used either in a liquid or a vapor form, or acombination thereof. The diluent is either added directly to a feedstockentering into a reactor or added directly into a reactor, or added witha molecular sieve catalyst composition. In one embodiment, the amount ofdiluent in the feedstock is in the range of from about 1 to about 99mole percent based on the total number of moles of the feedstock anddiluent, preferably from about 1 to 80 mole percent, more preferablyfrom about 5 to about 50, and most preferably from about 5 to about 25.

In one embodiment, other hydrocarbons are added to a feedstock eitherdirectly or indirectly, and include olefin(s), paraffin(s), aromatic(s)(see for example U.S. Pat. No. 4,677,242, addition of aromatics) ormixtures thereof, preferably propylene, butylene, pentylene, and otherhydrocarbons having 4 or more carbon atoms, or mixtures thereof.

The process for converting a feedstock, especially a feedstockcontaining one or more oxygenates, in the presence of a molecular sievecatalyst composition of the invention, is carried out in a reactionprocess in a reactor, where the process is a fixed bed process, afluidized bed process (includes a turbulent bed process), preferably acontinuous fluidized bed process, and most preferably a continuous highvelocity fluidized bed process.

The reaction processes can take place in a variety of catalytic reactorssuch as hybrid reactors that have a dense bed or fixed bed reactionzones and/or fast fluidized bed reaction zones coupled together,circulating fluidized bed reactors, riser reactors, and the like.Suitable conventional reactor types are described in for example U.S.Pat. No. 4,076,796, U.S. Pat. No. 6,287,522 (dual riser), andFluidization Engineering, D. Kunii and O. Levenspiel, Robert E. KriegerPublishing Company, New York, N.Y. 1977, which are all herein fullyincorporated by reference. The preferred reactor type are riser reactorsgenerally described in Riser Reactor, Fluidization and Fluid-ParticleSystems, pages 48 to 59, F. A. Zenz and D. F. Othmo, Reinhold PublishingCorporation, New York, 1960, and U.S. Pat. No. 6,166,282 (fast-fluidizedbed reactor), and U.S. patent application Ser. No. 09/564,613 filed May4, 2000 (multiple riser reactor), which are all herein fullyincorporated by reference.

In the preferred embodiment, a fluidized bed process or high velocityfluidized bed process includes a reactor system, a regeneration systemand a recovery system.

The reactor system preferably is a fluid bed reactor system having afirst reaction zone within one or more riser reactor(s) and a secondreaction zone within at least one disengaging vessel, preferablycomprising one or more cyclones. In one embodiment, the one or moreriser reactor(s) and disengaging vessel is contained within a singlereactor vessel. Fresh feedstock, preferably containing one or moreoxygenates, optionally with one or more diluent(s), is fed to the one ormore riser reactor(s) in which a molecular sieve catalyst composition orcoked version thereof is introduced. In one embodiment, the molecularsieve catalyst composition or coked version thereof is contacted with aliquid or gas, or combination thereof, prior to being introduced to theriser reactor(s), preferably the liquid is water or methanol, and thegas is an inert gas such as nitrogen.

In an embodiment, the amount of fresh feedstock fed separately orjointly with a vapor feedstock, to a reactor system is in the range offrom 0.1 weight percent to about 85 weight percent, preferably fromabout 1 weight percent to about 75 weight percent, more preferably fromabout 5 weight percent to about 65 weight percent based on the totalweight of the feedstock including any diluent contained therein. Theliquid and vapor feedstocks are preferably the same composition, orcontain varying proportions of the same or different feedstock with thesame or different diluent.

The feedstock entering the reactor system is preferably converted,partially or fully, in the first reactor zone into a gaseous effluentthat enters the disengaging vessel along with a coked molecular sievecatalyst composition. In the preferred embodiment, cyclone(s) within thedisengaging vessel are designed to separate the molecular sieve catalystcomposition, preferably a coked molecular sieve catalyst composition,from the gaseous effluent containing one or more olefin(s) within thedisengaging zone. Cyclones are preferred, however, gravity effectswithin the disengaging vessel will also separate the catalystcompositions from the gaseous effluent. Other methods for separating thecatalyst compositions from the gaseous effluent include the use ofplates, caps, elbows, and the like.

In one embodiment of the disengaging system, the disengaging systemincludes a disengaging vessel, typically a lower portion of thedisengaging vessel is a stripping zone. In the stripping zone the cokedmolecular sieve catalyst composition is contacted with a gas, preferablyone or a combination of steam, methane, carbon dioxide, carbon monoxide,hydrogen, or an inert gas such as argon, preferably steam, to recoveradsorbed hydrocarbons from the coked molecular sieve catalystcomposition that is then introduced to the regeneration system. Inanother embodiment, the stripping zone is in a separate vessel from thedisengaging vessel and the gas is passed at a gas hourly superficialvelocity (GHSV) of from 1 hr⁻¹ to about 20,000 hr⁻¹ based on the volumeof gas to volume of coked molecular sieve catalyst composition,preferably at an elevated temperature from 250° C. to about 750° C.,preferably from about 350° C. to 650° C., over the coked molecular sievecatalyst composition.

The conversion temperature employed in the conversion process,specifically within the reactor system, is in the range of from about200° C. to about 1000° C., preferably from about 250° C. to about 800°C., more preferably from about 250° C. to about 750° C., yet morepreferably from about 300° C. to about 650° C., yet even more preferablyfrom about 350° C. to about 600° C. most preferably from about 350° C.to about 550° C.

The conversion pressure employed in the conversion process, specificallywithin the reactor system, varies over a wide range including autogenouspressure. The conversion pressure is based on the partial pressure ofthe feedstock exclusive of any diluent therein. Typically the conversionpressure employed in the process is in the range of from about 0.1 kPaato about 5 MPaa, preferably from about 5 kPaa to about 1 MPaa, and mostpreferably from about 20 kPaa to about 500 kPaa.

The weight hourly space velocity (WHSV), particularly in a process forconverting a feedstock containing one or more oxygenates in the presenceof a molecular sieve catalyst composition within a reaction zone, isdefined as the total weight of the feedstock excluding any diluents tothe reaction zone per hour per weight of molecular sieve in themolecular sieve catalyst composition in the reaction zone. The WHSV ismaintained at a level sufficient to keep the catalyst composition in afluidized state within a reactor.

Typically, the WHSV ranges from about 1 hr⁻¹ to about 5000 hr⁻¹,preferably from about 2 hr⁻¹ to about 3000 hr⁻¹, more preferably fromabout 5 hr⁻¹ to about 1500 hr⁻¹, and most preferably from about 10 hr⁻¹to about 1000 hr⁻¹. In one preferred embodiment, the WHSV is greaterthan 20 hr⁻¹, preferably the WHSV for conversion of a feedstockcontaining methanol and dimethyl ether is in the range of from about 20hr⁻¹ to about 300 hr⁻¹.

The superficial gas velocity (SGV) of the feedstock including diluentand reaction products within the reactor system is preferably sufficientto fluidize the molecular sieve catalyst composition within a reactionzone in the reactor. The SGV in the process, particularly within thereactor system, more particularly within the riser reactor(s), is atleast 0.1 meter per second (m/sec), preferably greater than 0.5 m/sec,more preferably greater than 1 m/sec, even more preferably greater than2 m/sec, yet even more preferably greater than 3 m/sec, and mostpreferably greater than 4 m/sec. See for example U.S. patent applicationSer. No. 09/708,753 filed Nov. 8, 2000, which is herein incorporated byreference.

In one preferred embodiment of the process for converting an oxygenateto olefin(s) using a silicoaluminophosphate molecular sieve catalystcomposition, the process is operated at a WHSV of at least 20 hr⁻¹ and aTemperature Corrected Normalized Methane Selectivity (TCNMS) of lessthan 0.016, preferably less than or equal to 0.01. See for example U.S.Pat. No. 5,952,538, which is herein fully incorporated by reference. Inanother embodiment of the processes for converting an oxygenate such asmethanol to one or more olefin(s) using a molecular sieve catalystcomposition, the WHSV is from 0.01 hr⁻¹ to about 100 hr⁻¹, at atemperature of from about 350° C. to 550° C., and silica to Me₂O₃ (Me isa Group IIIA or VIII element from the Periodic Table of Elements) molarratio of from 300 to 2500. See for example EP-0 642 485 B1, which isherein fully incorporated by reference. Other processes for convertingan oxygenate such as methanol to one or more olefin(s) using a molecularsieve catalyst composition are described in PCT WO 01/23500 publishedApr. 5, 2001 (propane reduction at an average catalyst feedstockexposure of at least 1.0), which is herein incorporated by reference.

The coked molecular sieve catalyst composition is withdrawn from thedisengaging vessel, preferably by one or more cyclones(s), andintroduced to the regeneration system. The regeneration system comprisesa regenerator where the coked catalyst composition is contacted with aregeneration medium, preferably a gas containing oxygen, under generalregeneration conditions of temperature, pressure and residence time.Non-limiting examples of the regeneration medium include one or more ofoxygen, O₃, SO₃, N₂O, NO, NO₂, N₂O₅, air, air diluted with nitrogen orcarbon dioxide, oxygen and water (U.S. Pat. No. 6,245,703), carbonmonoxide and/or hydrogen. The regeneration conditions are those capableof burning coke from the coked catalyst composition, preferably to alevel less than 0.5 weight percent based on the total weight of thecoked molecular sieve catalyst composition entering the regenerationsystem. The coked molecular sieve catalyst composition withdrawn fromthe regenerator forms a regenerated molecular sieve catalystcomposition.

The regeneration temperature is in the range of from about 200° C. toabout 1500° C., preferably from about 300° C. to about 1000° C., morepreferably from about 450° C. to about 750° C., and most preferably fromabout 550° C. to 700° C. The regeneration pressure is in the range offrom about 15 psia (103 kpaa) to about 500 psia (3448 kPaa), preferablyfrom about 20 psia (138 kPaa) to about 250 psia (1724 kpaa), morepreferably from about 25 psia (172 kPaa) to about 150 psia (1034 kpaa),and most preferably from about 30 psia (207 kPaa) to about 60 psia (414kPaa). The preferred residence time of the molecular sieve catalystcomposition in the regenerator is in the range of from about one minuteto several hours, most preferably about one minute to 100 minutes, andthe preferred volume of oxygen in the gas is in the range of from about0.01 mole percent to about 5 mole percent based on the total volume ofthe gas.

In one embodiment, regeneration promoters, typically metal containingcompounds such as platinum, palladium and the like, are added to theregenerator directly, or indirectly, for example with the coked catalystcomposition. Also, in another embodiment, a fresh molecular sievecatalyst composition is added to the regenerator containing aregeneration medium of oxygen and water as described in U.S. Pat. No.6,245,703, which is herein fully incorporated by reference. In yetanother embodiment, a portion of the coked molecular sieve catalystcomposition from the regenerator is returned directly to the one or moreriser reactor(s), or indirectly, by pre-contacting with the feedstock,or contacting with fresh molecular sieve catalyst composition, orcontacting with a regenerated molecular sieve catalyst composition or acooled regenerated molecular sieve catalyst composition described below.

The burning of coke is an exothermic reaction, and in an embodiment, thetemperature within the regeneration system is controlled by varioustechniques in the art including feeding a cooled gas to the regeneratorvessel, operated either in a batch, continuous, or semi-continuous mode,or a combination thereof. A preferred technique involves withdrawing theregenerated molecular sieve catalyst composition from the regenerationsystem and passing the regenerated molecular sieve catalyst compositionthrough a catalyst cooler that forms a cooled regenerated molecularsieve catalyst composition. The catalyst cooler, in an embodiment, is aheat exchanger that is located either internal or external to theregeneration system. In one embodiment, the cooler regenerated molecularsieve catalyst composition is returned to the regenerator in acontinuous cycle, alternatively, (see U.S. patent application Ser. No.09/587,766 filed Jun. 6, 2000) a portion of the cooled regeneratedmolecular sieve catalyst composition is returned to the regeneratorvessel in a continuous cycle, and another portion of the cooledmolecular sieve regenerated molecular sieve catalyst composition isreturned to the riser reactor(s), directly or indirectly, or a portionof the regenerated molecular sieve catalyst composition or cooledregenerated molecular sieve catalyst composition is contacted withby-products within the gaseous effluent (PCT WO 00/49106 published Aug.24, 2000), which are all herein fully incorporated by reference. Inanother embodiment, a regenerated molecular sieve catalyst compositioncontacted with an alcohol, preferably ethanol, 1-propnaol, 1-butanol ormixture thereof, is introduced to the reactor system, as described inU.S. patent application Ser. No. 09/785,122 filed Feb. 16, 2001, whichis herein fully incorporated by reference. Other methods for operating aregeneration system are in disclosed U.S. Pat. No. 6,290,916(controlling moisture), which is herein fully incorporated by reference.

The regenerated molecular sieve catalyst composition withdrawn from theregeneration system, preferably from the catalyst cooler, is combinedwith a fresh molecular sieve catalyst composition and/or re-circulatedmolecular sieve catalyst composition and/or feedstock and/or fresh gasor liquids, and returned to the riser reactor(s). In another embodiment,the regenerated molecular sieve catalyst composition withdrawn from theregeneration system is returned to the riser reactor(s) directly,preferably after passing through a catalyst cooler. In one embodiment, acarrier, such as an inert gas, feedstock vapor, steam or the like,semi-continuously or continuously, facilitates the introduction of theregenerated molecular sieve catalyst composition to the reactor system,preferably to the one or more riser reactor(s).

By controlling the flow of the regenerated molecular sieve catalystcomposition or cooled regenerated molecular sieve catalyst compositionfrom the regeneration system to the reactor system, the optimum level ofcoke on the molecular sieve catalyst composition entering the reactor ismaintained. There are many techniques for controlling the flow of amolecular sieve catalyst composition described in Michael Louge,Experimental Techniques, Circulating Fluidized Beds, Grace, Avidan andKnowlton, eds., Blackie, 1997 (336-337), which is herein incorporated byreference. Coke levels on the molecular sieve catalyst composition ismeasured by withdrawing from the conversion process the molecular sievecatalyst composition at a point in the process and determining itscarbon content. Typical levels of coke on the molecular sieve catalystcomposition, after regeneration is in the range of from 0.01 weightpercent to about 15 weight percent, preferably from about 0.1 weightpercent to about 10 weight percent, more preferably from about 0.2weight percent to about 5 weight percent, and most preferably from about0.3 weight percent to about 2 weight percent based on the total weightof the molecular sieve and not the total weight of the molecular sievecatalyst composition.

In one preferred embodiment, the mixture of fresh molecular sievecatalyst composition and regenerated molecular sieve catalystcomposition and/or cooled regenerated molecular sieve catalystcomposition contains in the range of from about 1 to 50 weight percent,preferably from about 2 to 30 weight percent, more preferably from about2 to about 20 weight percent, and most preferably from about 2 to about10 coke or carbonaceous deposit based on the total weight of the mixtureof molecular sieve catalyst compositions. See for example U.S. Pat. No.6,023,005, which is herein fully incorporated by reference.

The gaseous effluent is withdrawn from the disengaging system and ispassed through a recovery system. There are many well known recoverysystems, techniques and sequences that are useful in separatingolefin(s) and purifying olefin(s) from the gaseous effluent. Recoverysystems generally comprise one or more or a combination of a variousseparation, fractionation and/or distillation towers, columns,splitters, or trains, reaction systems such as ethylbenzene manufacture(U.S. Pat. No. 5,476,978) and other derivative processes such asaldehydes, ketones and ester manufacture (U.S. Pat. No. 5,675,041), andother associated equipment for example various condensers, heatexchangers, refrigeration systems or chill trains, compressors,knock-out drums or pots, pumps, and the like. Non-limiting examples ofthese towers, columns, splitters or trains used alone or in combinationinclude one or more of a demethanizer, preferably a high temperaturedemethanizer, a dethanizer, a depropanizer, preferably a wetdepropanizer, a wash tower often referred to as a caustic wash towerand/or quench tower, absorbers, adsorbers, membranes, ethylene (C2)splitter, propylene (C3) splitter, butene (C4) splitter, and the like.

Various recovery systems useful for recovering predominately olefin(s),preferably prime or light olefin(s) such as ethylene, propylene and/orbutene are described in U.S. Pat. No. 5,960,643 (secondary rich ethylenestream), U.S. Pat. Nos. 5,019,143, 5,452,581 and 5,082,481 (membraneseparations), U.S. Pat. No. 5,672,197 (pressure dependent adsorbents),U.S. Pat. No. 6,069,288 (hydrogen removal), U.S. Pat. No. 5,904,880(recovered methanol to hydrogen and carbon dioxide in one step), U.S.Pat. No. 5,927,063 (recovered methanol to gas turbine power plant), andU.S. Pat. No. 6,121,504 (direct product quench), U.S. Pat. No. 6,121,503(high purity olefins without superfractionation), and U.S. Pat. No.6,293,998 (pressure swing adsorption), which are all herein fullyincorporated by reference.

Generally accompanying most recovery systems is the production,generation or accumulation of additional products, by-products and/orcontaminants along with the preferred prime products. The preferredprime products, the light olefins, such as ethylene and propylene, aretypically purified for use in derivative manufacturing processes such aspolymerization processes. Therefore, in the most preferred embodiment ofthe recovery system, the recovery system also includes a purificationsystem. For example, the light olefin(s) produced particularly in a MTOprocess are passed through a purification system that removes low levelsof by-products or contaminants. Non-limiting examples of contaminantsand by-products include generally polar compounds such as water,alcohols, carboxylic acids, ethers, carbon oxides, sulfur compounds suchas hydrogen sulfide, carbonyl sulfides and mercaptans, ammonia and othernitrogen compounds, arsine, phosphine and chlorides. Other contaminantsor by-products include hydrogen and hydrocarbons such as acetylene,methyl acetylene, propadiene, butadiene and butyne.

Other recovery systems that include purification systems, for examplefor the purification of olefin(s), are described in Kirk-OthmerEncyclopedia of Chemical Technology, 4th Edition, Volume 9, John Wiley &Sons, 1996, pages 249-271 and 894-899, which is herein incorporated byreference. Purification systems are also described in for example, U.S.Pat. No. 6,271,428 (purification of a diolefin hydrocarbon stream), U.S.Pat. No. 6,293,999 (separating propylene from propane), and U.S. patentapplication Ser. No. 09/689,363 filed Oct. 20, 2000 (purge stream usinghydrating catalyst), which is herein incorporated by reference.

Typically, in converting one or more oxygenates to olefin(s) having 2 or3 carbon atoms, an amount of hydrocarbons, particularly olefin(s),especially olefin(s) having 4 or more carbon atoms, and otherby-products are formed or produced. Included in the recovery systems ofthe invention are reaction systems for converting the products containedwithin the effluent gas withdrawn from the reactor or converting thoseproducts produced as a result of the recovery system utilized.

In one embodiment, the effluent gas withdrawn from the reactor is passedthrough a recovery system producing one or more hydrocarbon containingstream(s), in particular, a three or more carbon atom (C₃ ⁺) hydrocarboncontaining stream. In this embodiment, the C₃ ⁺ hydrocarbon containingstream is passed through a first fractionation zone producing a crude C₃hydrocarbon and a C₄ ⁺ hydrocarbon containing stream, the C₄ ⁺hydrocarbon containing stream is passed through a second fractionationzone producing a crude C₄ hydrocarbon and a C₅ ⁺ hydrocarbon containingstream. The four or more carbon hydrocarbons include butenes such asbutene-1 and butene-2, butadienes, saturated butanes, and isobutanes.

The effluent gas removed from a conversion process, particularly a MTOprocess, typically has a minor amount of hydrocarbons having 4 or morecarbon atoms. The amount of hydrocarbons having 4 or more carbon atomsis typically in an amount less than 20 weight percent, preferably lessthan 10 weight percent, more preferably less than 5 weight percent, andmost preferably less than 2 weight percent, based on the total weight ofthe effluent gas withdrawn from a MTO process, excluding water. Inparticular with a conversion process of oxygenates into olefin(s)utilizing a molecular sieve catalyst composition the resulting effluentgas typically comprises a majority of ethylene and/or propylene and aminor amount of four carbon and higher carbon number products and otherby-products, excluding water.

Suitable well known reaction systems as part of the recovery systemprimarily take lower value products and convert them to higher valueproducts. For example, the C₄ hydrocarbons, butene-1 and butene-2 areused to make alcohols having 8 to 13 carbon atoms, and other specialtychemicals, isobutylene is used to make a gasoline additive,methyl-t-butylether, butadiene in a selective hydrogenation unit isconverted into butene-1 and butene-2, and butane is useful as a fuel.Non-limiting examples of reaction systems include U.S. Pat. No.5,955,640 (converting a four carbon product into butene-1), U.S. Pat.No. 4,774,375 (isobutane and butene-2 oligomerized to an alkylategasoline), U.S. Pat. No. 6,049,017 (dimerization of n-butylene), U.S.Pat. Nos. 4,287,369 and 5,763,678 (carbonylation or hydroformulation ofhigher olefins with carbon dioxide and hydrogen making carbonylcompounds), U.S. Pat. No. 4,542,252 (multistage adiabatic process), U.S.Pat. No. 5,634,354 (olefin-hydrogen recovery), and Cosyns, J. et al.,Process for Upgrading C3, C4 and C5 Olefinic Streams, Pet. & Coal, Vol.37, No. 4 (1995) (dimerizing or oligomerizing propylene, butylene andpentylene), which are all herein fully incorporated by reference.

The preferred light olefin(s) produced by any one of the processesdescribed above, preferably conversion processes, are high purity primeolefin(s) products that contains a single carbon number olefin in anamount greater than 80 percent, preferably greater than 90 weightpercent, more preferably greater than 95 weight percent, and mostpreferably no less than about 99 weight percent, based on the totalweight of the olefin. In one embodiment, high purity prime olefin(s) areproduced in the process of the invention at rate of greater than 5 kgper day, preferably greater than 10 kg per day, more preferably greaterthan 20 kg per day, and most preferably greater than 50 kg per day. Inanother embodiment, high purity ethylene and/or high purity propylene isproduced by the process of the invention at a rate greater than 4,500 kgper day, preferably greater than 100,000 kg per day, more preferablygreater than 500,000 kg per day, even more preferably greater than1,000,000 kg per day, yet even more preferably greater than 1,500,000 kgper day, still even more preferably greater than 2,000,000 kg per day,and most preferably greater than 2,500,000 kg per day.

Other conversion processes, in particular, a conversion process of anoxygenate to one or more olefin(s) in the presence of a molecular sievecatalyst composition, especially where the molecular sieve issynthesized from a silicon-, phosphorous-, and alumina-source, includethose described in for example: U.S. Pat. No. 6,121,503 (making plasticwith an olefin product having a paraffin to olefin weight ratio lessthan or equal to 0.05), U.S. Pat. No. 6,187,983 (electromagnetic energyto reaction system), PCT WO 99/18055 publishes Apr. 15, 1999 (heavyhydrocarbon in effluent gas fed to another reactor) PCT WO 01/60770published Aug. 23, 2001 and U.S. patent application Ser. No. 09/627,634filed Jul. 28, 2000 (high pressure), U.S. patent application Ser. No.09/507,838 filed Feb. 22, 2000 (staged feedstock injection), and U.S.patent application Ser. No. 09/785,409 filed Feb. 16, 2001 (acetoneco-fed), which are all herein fully incorporated by reference.

In an embodiment, an integrated process is directed to producing lightolefin(s) from a hydrocarbon feedstock, preferably a hydrocarbon gasfeedstock, more preferably methane and/or ethane. The first step in theprocess is passing the gaseous feedstock, preferably in combination witha water stream, to a syngas production zone to produce a synthesis gas(syngas) stream. Syngas production is well known, and typical syngastemperatures are in the range of from about 700° C. to about 1200° C.and syngas pressures are in the range of from about 2 MPa to about 100MPa. Synthesis gas streams are produced from natural gas, petroleumliquids, and carbonaceous materials such as coal, recycled plastic,municipal waste or any other organic material, preferably synthesis gasstream is produced via steam reforming of natural gas. Generally, aheterogeneous catalyst, typically a copper based catalyst, is contactedwith a synthesis gas stream, typically carbon dioxide and carbonmonoxide and hydrogen to produce an alcohol, preferably methanol, oftenin combination with water. In one embodiment, the synthesis gas streamat a synthesis temperature in the range of from about 150° C. to about450° C. and at a synthesis pressure in the range of from about 5 MPa toabout 10 MPa is passed through a carbon oxide conversion zone to producean oxygenate containing stream.

This oxygenate containing stream, or crude methanol, typically containsthe alcohol product and various other components such as ethers,particularly dimethyl ether, ketones, aldehydes, dissolved gases such ashydrogen methane, carbon oxide and nitrogen, and fusel oil. Theoxygenate containing stream, crude methanol, in the preferred embodimentis passed through a well known purification processes, distillation,separation and fractionation, resulting in a purified oxygenatecontaining stream, for example, commercial Grade A and AA methanol. Theoxygenate containing stream or purified oxygenate containing stream,optionally with one or more diluents, is contacted with one or moremolecular sieve catalyst composition described above in any one of theprocesses described above to produce a variety of prime products,particularly light olefin(s), ethylene and/or propylene. Non-limitingexamples of this integrated process is described in EP-B-0 933 345,which is herein fully incorporated by reference. In another more fullyintegrated process, optionally with the integrated processes describedabove, olefin(s) produced are directed to, in one embodiment, one ormore polymerization processes for producing various polyolefins. (Seefor example U.S. patent application Ser. No. 09/615,376 filed Jul. 13,2000, which is herein fully incorporated by reference.)

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure processes, or a combination thereof. Particularlypreferred is a gas phase or a slurry phase polymerization of one or moreolefin(s) at least one of which is ethylene or propylene. Thesepolymerization processes utilize a polymerization catalyst that caninclude any one or a combination of the molecular sieve catalystsdiscussed above, however, the preferred polymerization catalysts arethose Ziegler-Natta, Phillips-type, metallocene, metallocene-type andadvanced polymerization catalysts, and mixtures thereof. The polymersproduced by the polymerization processes described above include linearlow density polyethylene, elastomers, plastomers, high densitypolyethylene, low density polyethylene, polypropylene and polypropylenecopolymers. The propylene based polymers produced by the polymerizationprocesses include atactic polypropylene, isotactic polypropylene,syndiotactic polypropylene, and propylene random, block or impactcopolymers.

In preferred embodiment, the integrated process comprises a polymerizingprocess of one or more olefin(s) in the presence of a polymerizationcatalyst system in a polymerization reactor to produce one or morepolymer products, wherein the one or more olefin(s) having been made byconverting an alcohol, particularly methanol, using a molecular sievecatalyst composition. The preferred polymerization process is a gasphase polymerization process and at least one of the olefins(s) iseither ethylene or propylene, and preferably the polymerization catalystsystem is a supported metallocene catalyst system. In this embodiment,the supported metallocene catalyst system comprises a support, ametallocene or metallocene-type compound and an activator, preferablythe activator is a non-coordinating anion or alumoxane, or combinationthereof, and most preferably the activator is alumoxane.

In addition to polyolefins, numerous other olefin derived products areformed from the olefin(s) recovered any one of the processes describedabove, particularly the conversion processes, more particularly the GTOprocess or MTO process. These include, but are not limited to,aldehydes, alcohols, acetic acid, linear alpha olefins, vinyl acetate,ethylene dicholoride and vinyl chloride, ethylbenzene, ethylene oxide,cumene, isopropyl alcohol, acrolein, allyl chloride, propylene oxide,acrylic acid, ethylene-propylene rubbers, and acrylonitrile, and trimersand dimers of ethylene, propylene or butylenes.

EXAMPLES

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples areoffered. Constituents of a mixture used for formulating catalysts willgenerally contain volatile components, including, but not limited to,water and, in the case of molecular sieve, organic template. It iscommon practice to describe the amount or proportion of theseconstituents as being on a “calcined basis”. Calcination involvesheating a material in the presence of air at an elevated temperaturesufficient to dry and remove any contained volatile content (650° C. forone or more hours). On a “calcined basis” is defined, for the purposesof the current invention, as the amount or fraction of each componentremaining after it has been mathematically reduced to account for lossesin weight expected to occur if the component had been calcined. Thus, 10grams of a component containing 25% volatiles would be described as “7.5g on a calcined basis”. Synthesis of a SAPO-34 molecular sieve is wellknown, and in the Examples below has a MSA of about 450 m²/g to 550m²/g-molecular sieve.

Micropore surface area (MSA) is a measurement of the amount ofmicropores present in a porous material. MSA is the difference betweenthe total surface area-BET surface area determined from relativepressures that gives a linear plot and the external surface area,calculated from the slope of the linear region of the t-plot with asmall correction to put it on the same basis as the BET surface area.This approach has been used for determining the amount of zeolite incracking catalysts by Johnson [M. F. L. Johnson, J. Catal., 52, 425-431(1978)]. The t-plot is a transformation of the adsorption isotherm inwhich relative pressure is replaced by t, the statistical thickness ofthe adsorbed layer on nonporous material at the corresponding relativepressure; see Lippens and de Boer for determining variouscharacteristics of pores systems, such as pore shapes [B. C. Lippens,and J. H. de Boer, J. Catal., 4, 319 (1965)]. Sing [K. S. W. Sing, Chem.Ind., 829 (1967)] has introduced that the extrapolation of a lineart-plot to t=0 can yield the volume of micropores.

MSA is determined using a MICROMERITICS Gemini 2375 from MicromeriticsInstrument Corporation, Norcross, Ga. is used. An amount, 0.15 g to 0.6g, of the sample was loaded into the sample cell for degassing at 300°C. for a minimum of 2 hours. During the analysis, the Evacuation Time is1.0 minute, no free spaced is used, and sample Density of 1.0 g/cc isused. Thirteen (13) adsorption data points are collected with adsorptiontargets of: Data Point Adsorption Target (p/p_(o)) 1 0.00500 2 0.07500 30.01000 4 0.05000 5 0.10000 6 0.15000 7 0.20000 8 0.25000 9 0.30000 100.40000 11 0.60000 12 0.75000 13 0.95000The correction factor used in the t-plot is 0.975. No de-sorption pointsare collected. Other analysis parameters include, Analysis Mode:Equilibrate; Equilibration Time: 5 second; Scan Rate:. 10 seconds. At-plot from 0.00000 to 0.90000 is constructed using the ASTM certifiedform of the Harkins and Jura equation (H-J Model):t(p)=(13.99/(0.034-log(p/p_(o))))_(0.5). It is shown by Cape and Kibby[J. A. Cape and C. L. Kibby, J. Colloids and Interface Science, 138,516-520 (1990)] that the conventional BET surface area of a microporousmaterial can be decomposed quantitatively into the external area and themicropore volume, as expressed by equation given below:S_(micro)=S_(tot)−S_(ext)=v_(m)/d_(j), where v_(m) is the microporevolume, S_(micro) is the micropore area calculated from S_(tot) andS_(ext). S_(tot) is given by the conventional BET method, and S_(ext) isthe external area taken from the t-plot. d_(j) is a nonphysical lengththe value of which depends on the pressure used in the experiments. Theproportionality factor, d_(j), is determined quantitatively by thepressures used in the BET fits.

Example 1

A slurry containing 45 wt % solid (on a calcined basis), 40% beingSAPO-34 molecular sieve, 10.6% Al₂O₃ (alumina sol, the binder), and49.4% clay (the matrix material), was prepared according to procedure:(A) add 2988.93 g of a SAPO-34 molecular sieve (on a calcined basis of1621.29 g) to 1703.84 g of deionized water, and mixed at 1500 RPM usinga Yamato 4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.)for 15 minutes, and then followed by a high-shear treatment using theSilverson high shear mixer L4RT-A at 6000 RPM for 10 minutes. Thisslurry had a pH value of 6.3 measured at 26° C. (B) ACH-Solution: add869.03 g (on a calcined basis of 429.64 g) of Reheis MicroDry aluminumchlorohydrate (Reheis Inc., Berkeley Heights, N.J.) to 859.12 g ofdeionized water and mixed at 1500 RPM using a Yamato 4000D mixer (YamatoScientific America Inc., Orangeburg, N.Y.) for 15 minutes followed by ahigh-shear treatment using the Silverson high shear mixer at 6000 RPMfor 10 minutes. This solution had a pH of 3.3 measured at 31° C. (C) theabove SAPO-34 molecular sieve slurry (A) and aluminum chlorohydratesolution (B) were combined and mixed at 1500 RPM using a Yamato 4000Dmixer (Yamato Scientific America Inc., Orangeburg, N.Y.) for 15 minutes,and then mixed using the Silverson high-shear mixer at 6000 RPM for 10minutes. This slurry had a pH value of 4.2 measured at 30° C. (D) add2302.3 g (on a calcined basis of 2002.30 g) of Engelhard's ASP Ultrafinekaolin clay (Engelhard Corporation, Iselin, N.J.) to the above slurrycontaining SAPO-34 molecular sieve and aluminum chlorohydrate underconstant mixing at 250 to 400 RPM, and then mixed at 1500 RPM using aYamato 4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.)for 15 minutes followed by a high-shear mixing step using the Silversonmixer at 6000 RPM for 10 minutes. (E) the solid content of the slurrywas adjusted to contain 45% solids, an amount of 283.97 g of deionizedwater was added to the above slurry containing SAPO-34 molecular sieve,ACH (the binder), and kaolin clay (the matrix material) followed with1500 RPM treatment for 15 minutes using the Yamato mixer and subsequenthigh-shear mixing using the Silverson mixer at 6000 RPM for 10 minutes.This final slurry had a pH value of 3.8 measured at 36° C. This led to8000 g of slurry containing 45% solids (on calcined basis), of which,40% being SAPO-34 molecular sieve, 10.6% being alumina binder, and 49.4%being clay matrix material. The weight ratio of the binder to themolecular sieve is about 0.265 and a MSA of 489.55 m²/g-molecular sieve.

Example 2

Spray drying of the slurry of Example 1 was conducted using a YamatoDL-41 spray dryer (Yamato Scientific America, Orangeburg, N.Y.). Anamount of 750 g of the slurry was spray dried. The spray dryer operatedin a down spray mode using an atomization nozzle of 1 mm. The spraydrying conditions were: feed rate: 40 g/min; inlet temperature: 350° C.;atomization pressure: 14 psig (96.5 kPag); carrier gas (nitrogen) flowat 60% of full setting. The spray dry product, the formulated molecularsieve catalyst composition was collected in a cyclone. The catalystcomposition was then calcined in a muffle furnace at 650° C. in air for2 hours. The calcined catalyst composition was used for attritiontesting and particle size analysis. Attrition resistance of the spraydried catalyst composition was determined using a jet-cup attritionunit. The hourly fines generation as a result of attrition thus obtainedis defined as the ARI. The higher the ARI the higher the attrition rateor the weaker or softer the formulated molecular sieve catalystcomposition. The molecular sieve catalyst composition of Example 1 spraydried in accordance with Example 2 had an ARI of 0.95 weight percent perhour.

Example 3

A slurry containing 45 wt % solid (on calcined basis), 40% being SAPO-34molecular sieve, 5.3% Al₂O₃ (the binder), and 54.7% clay (the matrixmaterial), was prepared according to the procedure: (A) add 332.1 g of aSAPO-34 molecular sieve (on a calcined basis of 180.01 g) to 201.82 g ofdeionized water that was mixed at 700 RPM using a Yamato 4000D mixer(Yamato Scientific America Inc., Orangeburg, N.Y.) for 10 minutes, thenfollowed by a high-shear treatment using the Silverson high shear mixerat 6000 RPM for 3 minutes. This slurry had a pH value of 6.9 measured at30° C. (B) ACH-Solution: add 48.28 g (on a calcined basis of 23.85 g) ofReheis MicroDry aluminum chlorohydrate (Reheis Inc., Berkeley Heights,N.J.) to 100.91 g of deionized water and mixed at 700 RPM using a Yamato4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.) for 7minutes, and then followed by a high-shear treatment using the Silversonhigh shear mixer at 6000 RPM for 3 minutes. This solution had a pH of4.0 measured at 25° C. (C) the above SAPO-34 slurry (A) and aluminumchlorohydrate solution (B) were combined, and mixed at 700 RPM using aYamato 4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.)for 10 minutes, and then mixed using the Silverson high-shear mixer at6000 RPM for 3 minutes. This slurry had a pH value of 4.2 measured at30° C. (D) add 283.28 g (on a calcined basis of 246.16 g) of Engelhard'sASP Ultrafine kaolin clay (the matrix material) (Engelhard Corporation,Iselin, N.J.) to the above slurry containing SAPO-34 molecular sieve andaluminum chlorohydrate (the binder) under constant mixing at 250 to 400RPM then mixed at 700 RPM using a Yamato 4000D mixer (Yamato ScientificAmerica Inc., Orangeburg, N.Y.) for 10 minutes, and followed by ahigh-shear mixing step using the Silverson mixer at 6000 RPM for 3minutes. (E) the solid content of the slurry was adjusted to contain 45%solids, an amount of 33.64 g of deionized water was added to the aboveslurry containing SAPO-34 molecular sieve, ACH solution, and kaolin clayfollowed with 700 RPM treatment for 15 minutes using the Yamato mixer,and subsequent high-shear mixing using the Silverson mixer at 6000 RPMfor 3 minutes. This final slurry had a pH value of 4.2 measured at 27°C. This led to 100 g of slurry containing 45% solids (on calcinedbasis), of which, 40% being SAPO-34 molecular sieve, 5.3% being aluminabinder, and 54.7% being clay matrix material. The slurry of this Example3 was then spray dried using the same procedure described in Example 2,in which the slurry of Example 1 was replaced with the slurry of Example3. The molecular sieve catalyst composition of Example 3 spray dried inaccordance with Example 2 had an ARI of 5.77 weight percent per hour.The weight ratio of the binder to the molecular sieve is about 0.13 anda MSA of 511.38 m²/g-molecular sieve.

Example 4

A slurry containing 45 wt % solid (on calcined basis), 40% being SAPO-34molecular sieve, 15.9% Al₂O₃ (the binder), and 44.1% clay (the matrixmaterial), was prepared according to the procedure: (A) add 332.1 g of aSAPO-34 molecular sieve (on a calcined basis of 180.00 g) to 176.82 gdeionized water and mixed at 700 RPM using a Yamato 4000D mixer (YamatoScientific America Inc., Orangeburg, N.Y.) for 10 minutes, and thenfollowed by a high-shear treatment using the Silverson high shear mixerat 6000 RPM for 3 minutes. This slurry had a pH value of 6.8 measured at31° C. (B) ACH-Solution: add 144.84 g (on a calcined basis of 71.55 g)of Reheis MicroDry aluminum chlorohydrate (the binder) (Reheis Inc.,Berkeley Heights, N.J.) to 88.41 g of deionized water, and mixed at 700RPM using a Yamato 4000D mixer (Yamato Scientific America Inc.,Orangeburg, N.Y.) for 7 minutes, and then followed by a high-sheartreatment using the Silverson high shear mixer at 6000 RPM for 3minutes. This solution had a pH of 3.1 measured at 32° C. (C) the aboveSAPO-34 molecular sieve slurry (A) and aluminum chlorohydrate solution(B) were combined, and mixed at 700 RPM using a Yamato 4000D mixer(Yamato Scientific America Inc., Orangeburg, N.Y.) for 10 minutes, thenfurther mixed using the Silverson high-shear mixer at 6000 RPM for 3minutes. This slurry had a pH value of 3.7 measured at 37° C. (D) add228.37 g (on a calcined basis of 198.45 g) of Engelhard's ASP Ultrafinekaolin clay (Engelhard Corporation, Iselin, N.J.) to the above slurrycontaining SAPO-34 molecular sieve and aluminum chlorohydrate underconstant mixing at 250 to 400 RPM was then mixed at 700 RPM using aYamato 4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.)for 10 minutes, and then followed by a high-shear mixing step using theSilverson mixer at 6000 RPM for 3 minutes. (E) the solid content of theslurry was adjusted to contain 45% solids, an amount of 29.47 g ofdeionized water was added to the above slurry containing SAPO-34molecular sieve, ACH solution, and kaolin clay followed with 700 RPMtreatment for 15 minutes using the Yamato mixer, and subsequenthigh-shear mixing using the Silverson mixer at 6000 RPM for 3 minutes.This final slurry had a pH value of 3.8 measured at 33° C. This led to1000 g of slurry containing 45% solids (on calcined basis), of which,40% being SAPO-34 molecular sieve, 15.9% being alumina binder, and 44.1%being clay matrix material. The slurry of this Example 4 was then spraydried using the same procedure described in Example 2, in which theslurry of Example 1 was replaced with the slurry of Example 4. Themolecular sieve catalyst composition of Example 4 spray dried inaccordance with Example 2 had an ARI of 0.38 weight percent per hour.The weight ratio of the binder to the molecular sieve is about 0.40 anda MSA of 470.08 m²/g-molecular sieve.

Example 5

A slurry containing 45 wt % solid (on calcined basis), 60% being SAPO-34molecular sieve, 7.1% Al₂O₃ (the binder), and 32.9% clay (the matrixmaterial), was prepared according to the procedure: (A) add 498.15 g ofa SAPO-34 molecular sieve (on a calcined basis of 270.00 g) to 160.08 gof deionized water, and then mixed at 700 RPM using a Yamato 4000D mixer(Yamato Scientific America Inc., Orangeburg, N.Y.) for 10 minutes, andthen followed by a high-shear treatment using the Silverson high shearmixer at 6000 RPM for 3 minutes. This slurry had a pH value of 6.6measured at 30° C. (B)

ACH-Solution: add 64.68 g (on a calcined basis of 31.95 g) of ReheisMicroDry aluminum chlorohydrate (the binder) (Reheis Inc., BerkeleyHeights, N.J.) to 80.04 g of deionized water, and then mixed at 700 RPMusing a Yamato 4000D mixer (Yamato Scientific America Inc., Orangeburg,N.Y.) for 7 minutes, and then followed by a high-shear treatment usingthe Silverson high shear mixer at 6000 RPM for 3 minutes. This solutionhad a pH of 3.6 measured at 26° C. (C) the above SAPO-34 molecular sieveslurry (A) and aluminum chlorohydrate solution (B) were combined, andthen mixed at 700 RPM using a Yamato 4000D mixer (Yamato ScientificAmerica Inc., Orangeburg, N.Y.) for 10 minutes, and then mixed using theSilverson high-shear mixer at 6000 RPM for 3 minutes. This slurry had apH value of 4.1 measured at 32° C. (D) add 170.37 g (on a calcined basisof 148.05 g) of Engelhard's ASP Ultrafine kaolin clay (EngelhardCorporation, Iselin, N.J.) to the above slurry containing SAPO-34molecular sieve and aluminum chlorohydrate (the binder) under constantmixing at 250 to 400 RPM, and then mixed at 700 RPM using a Yamato 4000Dmixer (Yamato Scientific America Inc., Orangeburg, N.Y.) for 10 minutes,and then followed by a high-shear mixing step using the Silverson mixerat 6000 RPM for 3 minutes. (E) the solid content of the slurry wasadjusted to contain 45% solids, an amount of 26.68 g of deionized waterwas added to the above slurry containing SAPO-34 molecular sieve, ACHsolution, and kaolin clay followed with 700 RPM treatment for 15 minutesusing the Yamato mixer, and subsequent high-shear mixing using theSilverson mixer at 6000 RPM for 3 minutes. This final slurry had a pHvalue of 3.9 measured at 32° C. This led to 1000 g of slurry containing45% solids (on calcined basis), of which, 40% being SAPO-34 molecularsieve, 7.1% being alumina binder, and 32.9% being clay matrix material.The slurry of this Example 5 was then spray dried using the sameprocedure described in Example 2, in which the slurry of Example 1 wasreplaced with the slurry of Example 5. The molecular sieve catalystcomposition of Example 5 spray dried in accordance with Example 2 had anARI of 12.54 weight percent per hour. The weight ratio of the binder tothe molecular sieve is about 0.12 and a MSA of 508.10 m²/g-molecularsieve.

Example 6

A slurry containing 45 wt % solid (on calcined basis), 20% being SAPO-34molecular sieve, 14.1% Al₂O₃ (the binder), and 65.9% clay (the matrixmaterial), was prepared according to the procedure: (A) add 166.05 g ofa SAPO-34 molecular sieve (on a calcined basis of 90.00 g) to 218.55 gof deionized water, mixed at 700 RPM using a Yamato 4000D mixer (YamatoScientific America Inc., Orangeburg, N.Y.) for 10 minutes, and followedby a high-shear treatment using the Silverson high shear mixer at 6000RPM for 3 minutes. This slurry had a pH value of 6.8 measured at 25° C.(B) ACH-Solution: add 128.44 g (on a calcined basis of 63.45 g) ofReheis MicroDry aluminum chlorohydrate (the binder) (Reheis Inc.,Berkeley Heights, N.J.) to 109.28 g of deionized water, and then mixedat 700 RPM using a Yamato 4000D mixer (Yamato Scientific America Inc.,Orangeburg, N.Y.) for 7 minutes, and then followed by a high-sheartreatment using the Silverson high shear mixer at 6000 RPM for 3minutes. This solution had a pH of 3.5 measured at 28° C. (C) the aboveSAPO-34 molecular sieve slurry (A) and aluminum chlorohydrate solution(B) were combined, and mixed at 700 RPM using a Yamato 4000D mixer(Yamato Scientific America Inc., Orangeburg, N.Y.) for 10 minutes, andthen mixed using the Silverson high-shear mixer at 6000 RPM for 3minutes. This slurry had a pH value of 4.0 measured at 28° C. (D) add341.25 g (on a calcined basis of 296.55 g) of Engelhard's ASP Ultrafinekaolin clay (Engelhard Corporation, Iselin, N.J.) to the above slurrycontaining SAPO-34 molecular sieve and aluminum chlorohydrate underconstant mixing at 250 to 400 RPM, and then mixed at 700 RPM using aYamato 4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.)for 10 minutes and then followed by a high-shear mixing step using theSilverson mixer at 6000 RPM for 3 minutes. (E) the solid content of theslurry was adjusted to contain 45% solids, an amount of 36.43 g ofdeionized water was added to the above slurry containing SAPO-34molecular sieve, ACH Solution, and kaolin clay followed with 700 RPMtreatment for 15 minutes using the Yamato mixer and subsequenthigh-shear mixing using the Silverson mixer at 6000 RPM for 3 minutes.This final slurry had a pH value of 3.7 measured at 31° C. This led to1000 g of slurry containing 45% solids (on calcined basis), of which,40% being SAPO-34 molecular sieve, 14.1% being alumina binder, and 65.9%being clay matrix material. The slurry of this Example 6 was then spraydried using the same procedure described in Example 2, in which theslurry of Example 1 was replaced with the slurry of Example 6. Themolecular sieve catalyst composition of Example 6 spray dried inaccordance with Example 2 had an ARI of 0.33 weight percent per hour.The weight ratio of the binder to the molecular sieve is about 0.71 anda MSA of 482.95 m²/g-molecular sieve.

Example 7

Conversion Process

Catalytic performance of a molecular sieve catalyst composition forconversion of methanol was conducted using a micro-reactor unit.Reaction conditions employed were: feed rate of 100 g-methanol per gramof molecular sieve; temperature of 475° C.; pressure of 25 psig (273kpag). A 35 mg of a catalyst composition of 2 to 200 microns in sizemixed with 100 mg of silicon carbide (100 microns, available fromCarborundum Abrasives G.B. Limited, Trafford Park, Manchester, UK) toform a mixture. This mixture was then loaded into a tubular reactor madeof 316 stainless steel with an internal diameter of 4 mm. The catalystcomposition bed is positioned in the middle section of the reactor bytwo quartz wool plugs on top and bottom of the catalyst composition bed.The catalyst composition was then treated in a helium flow at 50 cm³/min(STP) from 40° C. to 475° C. at ramp rate of 100° C./min and held at475° C. for 30 minutes before the methanol was introduced. Methanol(Fisher Scientific, Fair Lawn, N.J., 99.9% purity) is fed into avaporizer kept at 225° C. by a Cole-Palmer 74900 Series syringe pump ata feed rate of 29.59 ml per minute. Methanol flow was down flowedthrough the heated reactor tube. Gas phase products and unreactedmethanol were combined with 50 cm³/min (STP) helium at the outlet andperiodic samples were captured in an on-line sample storage (16-loop,150 ml/loop) valve. All the transfer lines and sampling valves were heattraced to 225° C. to prevent any condensation of unreacted methanol orproducts. The collected samples were then analyzed using an on-line GC(Hewlett Packard 6890 GC, Palo Alto, Calif.) equipped with an FIDdetector and a PLOT fused silica column (CP-PoraPLOT Q, 10 m×0.53 mmID×20 micron coating thickness, available from Varian, Inc, MitchellDr., Walnut Creek, Calif.). The reactor effluent was analyzed for:methane, methanol, dimethylether, ethane, ethylene, propane, propylene,isobutane, butene-1, cis-butene-2, and trans-butene-2, C₅ and higher, C₆and higher, C, and higher and C₈ and higher.

Conversion of methanol is defined as[(X_(CH3OH in feed)−X_(CH3OH in product))/X_(CH3OH in feed)]*100%;selectivity to each product component is defined as(X_(product)/X_(CH3OH in feed))*100, where X is the water free weightfraction of each component calculated from the FID signal. Cokeselectivity was estimated from a hydrogen balance of the feed andproducts. The product selectivity results reported are conversionweighted averages of the product selectivity over the entire experimentthat measures methanol conversion from an initial conversion ofapproximately 100% to a final conversion of approximately 10%.

Catalytic performance of the catalyst composition of Example 2 forconversion of methanol was evaluated using the process described aboveand showed a cumulative methanol converted per gram of molecular sieveof 12.6 g-methanol/g-molecular sieve and weight averaged ethylene andpropylene selectivity of 75.2%.

Catalytic performance of the catalyst composition of Example 4 forconversion of methanol was evaluated using the process described aboveand showed a cumulative methanol converted per gram of molecular sieveof 11.4 g-methanol/g-molecular sieve and weight averaged ethylene andpropylene selectivity of 74.3%.

Catalytic performance of the catalyst of Example 6 for conversion ofmethanol was evaluated using the process described and showed acumulative methanol converted per gram of molecular sieve of 12.4g-methanol/g-molecular sieve and weight averaged ethylene and propyleneselectivity of 74.6%.

Example 8

(50% Sieve, Binder/Molecular Sieve Ratio of 0.265)

A slurry containing 45 wt % solid (on a calcined basis), 50% beingSAPO-34 molecular sieve, 13.25% Al₂O₃ (alumina sol, the binder), and36.75% clay (the matrix material), was prepared according to procedure:(A) add 334.9 g of a SAPO-34 molecular sieve (on a calcined basis of180.0 g) to 212.9 g of deionized water, and mixed at 700 RPM using aYamato 4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.)for 10 minutes, and then followed by a high-shear treatment using theSilverson high shear mixer at 6000 RPM for 3 minutes. This slurry had apH value of 7.1 measured at 30° C. (B) add 96.9 g (on a calcined basisof 47.7 g) of Reheis MicroDry aluminum chlorohydrate (Reheis Inc.,Berkeley Heights, N.J.) the above SAPO-34 molecular sieve slurry (A),mixed at 700 RPM using a Yamato 4000D mixer (Yamato Scientific AmericaInc., Orangeburg, N.Y.) for 10 minutes, and then mixed using theSilverson high-shear mixer at 6000 RPM for 3 minutes. This slurry (C)had a pH value of 4.0 measured at 30° C. (D) add 155.6 g (on a calcinedbasis of 132.3 g) of Engelhard's ASP Ultrafine kaolin clay (EngelhardCorporation, Iselin, N.J.) to the above slurry containing SAPO-34molecular sieve and aluminum chlorohydrate under constant mixing at 250to 400 RPM, and then mixed at 700 RPM using a Yamato 4000D mixer (YamatoScientific America Inc., Orangeburg, N.Y.) for 10 minutes followed by ahigh-shear mixing step using the Silverson mixer at 6000 RPM for 3minutes. This final slurry had a pH value of 3.9 measured at 38° C. Thisled to 800.0 g of slurry containing 45% solids (on calcined basis), ofwhich, 50% being SAPO-34 molecular sieve, 13.25% being alumina binder,and 36.75% being clay matrix material. The weight ratio of the binder tothe molecular sieve is about 0.265 and a MSA of 498.82 m²/g-molecularsieve.

Example 9

Spray drying of the slurry of Example 8 was conducted using a YamatoDL-41 spray dryer (Yamato Scientific America, Orangeburg, N.Y.). Anamount of 800 g of the slurry was spray dried. The spray dryer operatedin a down spray mode using an atomization nozzle of 1 mm. The spraydrying conditions were: feed rate: 40 g/min; inlet temperature: 350° C.;atomization pressure: 14 psig (96.5 kPag); carrier gas (nitrogen) flowat 60% of full setting. The spray dry product, the formulated molecularsieve catalyst composition was collected in a cyclone. The catalystcomposition was then calcined in a muffle furnace at 650° C. in air for2 hours. The calcined catalyst composition was used for attritiontesting and particle size analysis. Attrition resistance of the spraydried catalyst composition was determined using a jet-cup attritionunit. The hourly fines generation as a result of attrition thus obtainedis defined as the ARI. The higher the ARI the higher the attrition rateor the weaker or softer the formulated molecular sieve catalystcomposition. The molecular sieve catalyst composition of Example 8 spraydried in accordance with Example 9 had an ARI of 0.24 weight percent perhour.

Example 10

(60% Sieve, Binder/Molecular Sieve Ratio of 0.265)

A slurry containing 45 wt % solid (on a calcined basis), 60% beingSAPO-34 molecular sieve, 15.9% Al₂O₃ (alumina sol, the binder), and24.1% clay (the matrix material), was prepared according to procedure:(A) add 854 g of a SAPO-34 molecular sieve (on a calcined basis of 459g) to 383 g of deionized water, and mixed at 700 RPM using a Yamato4000D mixer (Yamato Scientific America Inc., Orangeburg, N.Y.) for 10minutes, and then followed by a high-shear treatment using the Silversonhigh shear mixer at 6000 RPM for 3 minutes. This slurry had a pH valueof 6.5 measured at 29° C. (B) add 246.2 (on a calcined basis of 121.64g) of Reheis MicroDry aluminum chlorohydrate (Reheis Inc., BerkeleyHeights, N.J.) the above SAPO-34 molecular sieve slurry (A), mixed at700 RPM using a Yamato 4000D mixer (Yamato Scientific America Inc.,Orangeburg, N.Y.) for 10 minutes, and then mixed using the Silversonhigh-shear mixer at 6000 RPM for 3 minutes. This slurry (C) had a pHvalue of 3.54 measured at 30° C. (D) add 216.8 g (on a calcined basis of184.37 g) of Engelhard's ASP Ultrafine kaolin clay (EngelhardCorporation, Iselin, N.J.) to the above slurry containing SAPO-34molecular sieve and aluminum chlorohydrate under constant mixing at 250to 400 RPM, and then mixed at 700 RPM using a Yamato 4000D mixer (YamatoScientific America Inc., Orangeburg, N.Y.) for 19 minutes followed by ahigh-shear mixing step using the Silverson mixer at 6000 RPM for 3minutes. This final slurry had a pH value of 3.5 measured at 33° C. Thisled to 1700.0 g of slurry containing 45% solids (on calcined basis), ofwhich, 60% being SAPO-34 molecular sieve, 15.9% being alumina binder,and 24.1% being clay matrix material. The weight ratio of the binder tothe molecular sieve is about 0.265 and a MSA of 499.28 m²/g-molecularsieve.

Example 11

Spray drying of the slurry of Example 10 was conducted using a YamatoDL-41 spray dryer (Yamato Scientific America, Orangeburg, N.Y.). Anamount of 850 g of the slurry was spray dried. The spray dryer operatedin a down spray mode using an atomization nozzle of 1 mm. The spraydrying conditions were: feed rate: 40 g/min; inlet temperature: 350° C.;atomization pressure: 14 psig (96.5 kPag); carrier gas (nitrogen) flowat 60% of full setting. The spray dry product, the formulated molecularsieve catalyst composition was collected in a cyclone. The catalystcomposition was then calcined in a muffle furnace at 650° C. in air for2 hours. The calcined catalyst composition was used for attritiontesting and particle size analysis. Attrition resistance of the spraydried catalyst composition was determined using a jet-cup attritionunit. The hourly fines generation as a result of attrition thus obtainedis defined as the ARI. The higher the ARI the higher the attrition rateor the weaker or softer the formulated molecular sieve catalystcomposition. The molecular sieve catalyst composition of Example 10spray dried in accordance with Example 11 had an ARI of 0.23 weightpercent per hour.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that themolecular sieve catalyst composition is useful in the inter-conversionof olefin(s), oxygenate to gasoline conversions reactions, malaeicanhydride, phthalic anyhdride and acrylonitrile formulation, vapor phasemethanol synthesis, and various Fischer Tropsch reactions. It is furthercontemplated that a plug flow, fixed bed or fluidized bed process areused in combination, particularly in different reaction zones within asingle or multiple reactor system. It is also contemplated the molecularsieve catalyst compositions described herein are useful as absorbents,adsorbents, gas separators, detergents, water purifiers, and othervarious uses such as agriculture and horticulture. Additionallycontemplated the molecular sieve catalyst compositions include one ormore other molecular sieves in combination. For this reason, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

1-19. (canceled)
 20. A process for converting a feedstock into one ormore olefin(s) in the presence of a molecular sieve catalystcomposition, the molecular sieve catalyst composition comprising amolecular sieve and a binder, wherein the weight ratio of the binder tothe molecular sieve is greater than 0.1 to less than 0.5.
 21. Theprocess of claim 20, wherein the feedstock comprises oxygenates.
 22. Theprocess of claim 20, wherein the molecular sieve catalyst compositionhas an ARI less than 2 weight percent per hour.
 23. The process of claim20, wherein the weight ratio of the binder to the molecular sieve is inthe range of from 0.13 to about 0.45.
 24. The method of claim 20,wherein the molecular sieve catalyst composition further comprises amatrix material, and the binder is an alumina sol and the molecularsieve is a silicoaluminophosphate.
 25. A process for producing one ormore olefin(s), the process comprising the steps of: (a) introducing afeedstock to a reactor system in the presence of a molecular sievecatalyst composition comprising a molecular sieve, a binder, and amatrix material, wherein the weight ratio of the binder to the molecularsieve is in the range of greater than about 0.1 to 0.45; (b) withdrawingfrom the reactor system an effluent stream; and (c) passing the effluentgas through a recovery system recovering at least the one or moreolefin(s).
 26. The process of claim 25, wherein the process furthercomprises the step of: (d) introducing the molecular sieve catalystcomposition to a regeneration system to form a regenerated molecularsieve catalyst composition, and introducing the regenerated molecularsieve catalyst composition to the reaction system.
 27. The process ofclaim 25, wherein the feedstock comprises methanol, and the olefin(s)include ethylene and propylene, and the molecular sieve is asilicoaluminophosphate.
 28. The process of claim 25, wherein themolecular sieve catalyst composition has an ARI is less than 2 weightpercent per hour.
 29. The process of claim 28, wherein the molecularsieve catalyst composition has a MSA of at least 80% of the MSA of themolecular sieve, and the weight ratio of the binder to the molecularsieve is in the range of from 0.15 to 0.35.
 30. An integrated processfor making one or more olefin(s), the integrated process comprising thesteps of: (a) passing a hydrocarbon feedstock to a syngas productionzone to producing a synthesis gas stream; (b) contacting the synthesisgas stream with a catalyst to form an oxygenated feedstock; and (c)converting the oxygenated feedstock into the one or more olefin(s) inthe presence of a molecular sieve catalyst composition comprising amolecular sieve, a binder and a matrix material, wherein the weightratio of the binder to the molecular sieve is in the range of fromgreater than 0.1 to less than 0.45.
 31. The integrated process of claim30, wherein the process further comprises the step of: (d) polymerizingthe one or more olefin(s) in the presence of a polymerization catalystinto a polyolefin.
 32. The integrated process of claim 30, wherein theoxygenated feedstock comprises methanol, the olefin(s) include ethyleneand propylene, and the molecular sieve catalyst composition is asilicoaluminophosphate molecular sieve.
 33. The integrated process ofclaim 30, wherein the molecular sieve catalyst composition has an ARIless than 5 weight percent per hour.
 34. The integrated process of claim30, wherein the weight ratio of the binder to the molecular sieve is inthe range of from 0.14 to about 0.4. 35-40. (canceled)